Sulfonation of conducting polymers and oled, photovoltaic, and esd devices

ABSTRACT

Conducting polymer systems for hole injection or transport layer applications including a composition comprising: a water soluble or water dispersible regioregular polythiophene comprising (i) at least one organic substituent, and (ii) at least one sulfonate substituent comprising sulfonate sulfur bonding directly to the polythiophene backbone. The polythiophene can be water soluble, water dispersible, or water swellable. They can be self-doped. The organic substituent can be an alkoxy substituent, or an alkyl substituent. OLED, PLED, SMOLED, PV, and ESD applications can be used.

RELATED APPLICATIONS

This application claims priority to U.S. provisional application Ser.No. 60/832,095 filed on Jul. 21, 2006, which is incorporated byreference in its entirety, as well as to U.S. provisional applicationSer. No. 60/845,172 filed on Sep. 18, 2006, which is incorporated byreference in its entirety.

STATEMENT OF FEDERAL FUNDING SUPPORT

These inventions were made with Government support under Agreement No.DAAD19-02-3-001 awarded by Army Research Laboratory. The government hascertain rights in the inventions.

BACKGROUND

Although useful advances are being made in energy saving devices such asorganic-based organic light emitting diodes (OLEDs), polymer lightemitting diodes (PLEDs), and organic photovoltaic devices (OPVs),further improvements are still needed in providing better processing andperformance. For example, one promising type of material is conductingpolymers including for example polythiophenes and regioregularpolythiophenes, the latter first invented by Richard McCullough.However, problems can arise with doping, purity, and solubility andprocessing. In particular, it is important to have very good controlover the solubility of alternating layers of polymer (e.g., orthogonalor alternating solubility properties among adjacent layers). Inparticular, hole injection layers and hole transport layers can presentdifficult problems in view of competing demands and the need for verythin, but high quality, films.

A need exists for a good platform system to control properties of holeinjection and transport layers such as solubility and electronic energylevels like HOMO and LUMO, so that the materials can be adapted fordifferent applications and to function with different materials such aslight emitting layers, photoactive layers, and electrodes. Inparticular, good solubility properties are important, as well as thecontrol of energy levels like HOMO and LUMO and the ability to formulatethe system for a particular application and provide the required balanceof properties.

Polythiophenes and regioregular polythiophenes are particularlyimportant. Background references regarding polythiophenes include (1)Sotzing, G. A. Substituted thieno[3,4-b]thiophene polymers, method ofmaking and use thereof, US2005/0124784 A1; (2) Lee, B.; Seshadri, V.;Sotzing, G. A. Ring Sulfonated poly(thieno[3,4-b]thiophene), Adv. Mater.2005, 17, 1792. (3) Udman, Y. A.; Pekmez, K.; Yildiz, A. Synth. Met.2004, 142, 7. (4). Udman, Y. A.; Pekmez, K.; Yildiz, A. Eur. Poly. J.2004, 40, 1057. (5)“Method for producing soluble conductive polymershaving acidic groups” EP0834885B1.

Prior art often provides however important limits such as, for example,unstable doping, lack of solubility in starting polymers, lack ofversatility in formulation, lack of solvent control, limited fusedsystems, random sulfonation, lack of copolymerization, lack of controlof molecular weight, lack of structural control and regioregularity,lack of interaction between side group and conjugated chain, and alsolack of device data.

SUMMARY

Sulfonation and sulfonated polymers can be used to improve performanceand processes, particularly with polythiophenes and regioregularpolythiophenes. The various embodiments include compositions, methods ofmaking compositions, methods of using compositions, and devices. Forexample, one embodiment provides a composition comprising: a watersoluble or water dispersible regioregular polythiophene comprising (i)at least one organic substituent, and (ii) at least one sulfonatesubstituent comprising sulfonate sulfur bonding directly to thepolythiophene backbone.

Another embodiment is a composition comprising: a water soluble, waterdispersible, or water swellable regioregular polythiophene comprising(i) at least one organic substituent, and (ii) at least one sulfonatesubstituent comprising sulfonate sulfur bonding directly to thepolythiophene backbone. More generally, another embodiment provides acomposition comprising: a water soluble or water dispersibleregioregular heterocyclic polymer comprising (i) at least one organicsubstituent, and (ii) at least one sulfonate substituent comprisingsulfonate sulfur bonding directly to the polymer backbone. Theheterocyclic polymer can be for example a nitrogen-containing or asulfur-containing heterocyclic polymer.

Another embodiment comprises a method for making a compositioncomprising: reacting a soluble regioregular polythiophene comprising (i)at least one organic substituent with a sulfonation reagent so that thepolythiophene comprises at least one sulfonate substituent comprisingsulfonate sulfur bonding directly to the polythiophene backbone.

Another embodiment provides a coating composition comprising: (A) water,(B) a water soluble or water dispersible regioregular polythiophenecomprising (i) at least one organic substitutent, and (ii) at least onesulfonate substituent comprising sulfonate sulfur bonding directly tothe polythiophene backbone, and (C) a synthetic polymer different from(B). The composition can further comprise a water-miscible solvent.

Still further, also provided is a method of making a coating compositioncomprising: (A) providing water, (B) providing a water soluble orwater-dispersible regioregular polythiophene comprising (i) at least oneorganic substituent, and (ii) at least one sulfonate substituentcomprising sulfonate sulfur bonding directly to the polythiophenebackbone, (C) providing a synthetic polymer different from (B), (D)combining in any order (A), (B), and (C) to form a coating composition.The coating composition can also comprise a water-miscible solvent. Infurther steps, water can be removed to provide a coated surface orsubstrate.

Another embodiment is a coated substrate comprising: a solid surface, acoating disposed on the surface, wherein the coating comprises acomposition comprising: a water soluble, water dispersible, or waterswellable regioregular polythiophene comprising (i) at least one organicsubstituent, and (ii) at least one sulfonate substituent comprisingsulfonate sulfur bonding directly to the polythiophene backbone.

Still further, another embodiment is a coated substrate comprising: (B)a water soluble, water-dispersible, or water swellable regioregularpolythiophene comprising (i) at least one organic substituent, and (ii)at least one sulfonate substituent comprising sulfonate sulfur bondingdirectly to the polythiophene backbone, (C) a synthetic polymerdifferent from (B).

The films can show excellent stability including substantially no changein the UV-vis-NIR over seven days. The UV-vis-NIR spectra can also besensitive to pH which provides for applications.

Also provided are devices. For example, herein is provided a devicecomprising a layer comprising the composition comprising: a watersoluble or water dispersible regioregular polythiophene comprising (i)at least one organic substituent, and (ii) at least one sulfonatesubstituent comprising sulfonate sulfur bonding directly to thepolythiophene backbone. In one embodiment, the layer is a hole injectionlayer or a hole transport layer. The device can be for example an OLEDdevice, a PLED device, a SMOLED device, or a photovoltaic device. Thedevice can comprise at least two electrodes and at least one lightemitting or photoactive layer.

Another embodiment is a device comprising an electrostatic dissipation(ESD) material, said ESD material comprising at least one water solubleor water dispersible polymer comprising regioregular polythiophenecomprising: (i) at least one organic substituent; and (ii) at least onesulfonate substituent comprising sulfonate sulfur bonding directly tothe polythiophene backbone.

Another embodiment provides a method of reducing electrostatic charge ona device comprising coating said device with a coating comprising apolythiophene comprising: (i) at least one organic substituent; and (ii)at least one sulfonate substituent comprising sulfonate sulfur bondingdirectly to the polythiophene backbone.

Important aspects of one or more of these embodiments include that thedopant ion is present on the backbone of the polymer and hence migrationinto other components of the device is eliminated. The composition canbe totally free or substantially free of separately added small moleculeor polymeric dopants. In addition, the technology helps in altering theenergy levels of the polymer by merely varying the sulfonation levels onthe polymer backbone. Still further, donor and acceptor type polymer isprovided which has both the donor and acceptor functionality on the samerepeat unit. Another feature is that the polymer structure iswell-defined with alternating donor acceptors. Also important is amethod to convert an otherwise water insoluble polymer into watersoluble or water dispersible polymer. A method is also provided topurify the substance of free sulfuric acid by passing through strongbase type anion exchange resin (OH form). Another benefit comes from amethod by which the resultant sulfonated polymer is highly water solublemaking it easy to clean the reactor. Other advantages includeprocessable polymer, easy to make, and excellent orthogonalcompatibility with organic solvents.

Applications include for example hole injection layer for OLEDs, PLEDs,photovoltaic cells, electrostatic dissipation, supercapacitors, cationtransducers, drug release, electrochromics, sensors, FETs, actuators,and membranes.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates representative synthesis of sulfonated conjugatedpolymers.

FIG. 2 illustrates sulfonation of poly(3-methoxyethoxyethoxythiophene)using fuming sulfuric acid.

FIG. 3 illustrates conversion of sulfonic acid to sulfonate form.

FIG. 4 illustrates another embodiment with a dimerized thiophenemonomer.

FIG. 5 illustrates seven day stability data based on UV-Vis-NIR data.

FIG. 6 illustrates absorption spectra at two different pHs.

FIG. 7 illustrates a typical organic photovoltaic device.

FIG. 8 provides OPV data.

FIG. 9 illustrates a typical OLED device.

FIG. 10 illustrates device data indicative of HIL performance in OC1C10

FIG. 11 illustrates device data indicative of HIL performance inCommercial Emitter 1

FIG. 12 illustrates device data indicative of HIL performance inCommercial Emitter 2

FIG. 13 illustrates device data indicative of HIL performance in SMOLEDbased hybrid devices.

FIG. 14 illustrates lifetime data comparing PEDOT and HIL in SMOLEDbased hybrid devices.

FIG. 15 illustrates additional embodiments for polymers.

FIG. 16 illustrates degradation of power output of organic photovoltaiccells.

FIG. 17 illustrates current-voltage luminance performance.

FIG. 18 illustrates current-voltage luminance performance.

FIG. 19 illustrates luminance decay under passive matrix testingconditions.

FIG. 20 illustrates current-voltage-luminance performance.

FIG. 21 illustrates luminance decay under passive matrix testingconditions.

FIG. 22 illustrates current-voltage-luminance performance for SMOLEDdevices.

FIG. 23 illustrates comparison of luminance degradation for SMOLEDdevices.

DETAILED DESCRIPTION Introduction/Conducting Polymers and Polythiophenes

U.S. provisional patent application Ser. No. 60/832,095 “Sulfonation ofConducting Polymers and OLED and Photovoltaic Devices” filed Jul. 21,2006 to Seshadri et al. is hereby incorporated by reference in itsentirety including figures, working examples, and claims. In addition,U.S. provisional patent application Ser. No. 60/845,172 “Sulfonation ofConducting Polymers and OLED, Photovoltaic, and ESD Devices” filed Sep.18, 2006 to Seshadri et al. is hereby incorporated by reference in itsentirety including figures, working examples, and claims. Theseapplications describe the following 97 embodiments:

Embodiment 1

A composition comprising: a water soluble or water dispersibleregioregular polythiophene comprising (i) at least one organicsubstituent, and (ii) at least one sulfonated substituent comprisingsulfur bonding directly to the polythiophene backbone.

Embodiment 2

The composition according to embodiment 1, wherein the sulfonatedsubstituent is in acid form.

Embodiment 3

The composition according to embodiment 1, wherein the sulfonatedsubstituent is in salt form comprising a counterion.

Embodiment 4

The composition according to embodiment 1, wherein the sulfonatedsubstituent is in salt form comprising a counterion, wherein thecounterion comprises organic groups.

Embodiment 5

The composition according to embodiment 1, wherein the sulfonatedsubstituent is in salt form comprising a counterion, wherein thecounterion comprises an organic cation and is free of metal.

Embodiment 6

The composition according to embodiment 1, wherein the sulfonatedsubstituent is in salt form comprising a counterion, wherein thecounterion comprises a metal cation.

Embodiment 7

The composition according to embodiment 1, wherein the polythiophene isa regio regular head-to-tail coupled poly(3-substituted thiophene)having a degree of regioregularity of at least about 90% apart fromsulfonation.

Embodiment 8

The composition according to embodiment 1, wherein the polythiophene isa regio regular head to tail coupled poly(3-substituted thiophene)having a degree of regioregularity of at least about 98% apart fromsulfonation.

Embodiment 9

The composition according to embodiment 1, wherein the polythiophene iswater soluble.

Embodiment 10

The composition according to embodiment 1, wherein the polythiophene isdoped.

Embodiment 11

The composition according to embodiment 1, wherein the organicsubstituent comprises at least one heteroatom.

Embodiment 12

The composition according to embodiment 1, wherein the organicsubstituent is an alkoxy or alkyl substituent.

Embodiment 13

The composition according to embodiment 1, wherein the polythiophene isan alternating copolymer.

Embodiment 14

The composition according to embodiment 1, wherein the polythiophene isprepared from a bithiophene monomer.

Embodiment 15

The composition according to embodiment 1, wherein the polythiophene isa homopolymer of a thiophene, a copolymer comprising thiophene units, ora block copolymer comprising at least one block of polythiophene.

Embodiment 16

The composition according to embodiment 1, wherein the water soluble orwater dispersible regioregular polythiophene is in a crosslinked form.

Embodiment 17

The composition according to embodiment 1, wherein the polythiophene ischaracterized by a degree of sulfonation of about 50% to about 90%.

Embodiment 18

The composition according to embodiment 1, wherein polythiophene iswater soluble, the polythiophene is a homopolymer, and wherein theorganic substitutent is an alkoxy or alkyl substituent.

Embodiment 19

The composition according to embodiment 1, wherein the polythiophene iswater soluble, and wherein the polythiophene is in salt form comprisinga counterion, wherein the counterion comprises organic groups.

Embodiment 20

The composition according to embodiment 1, wherein the polythiophene iswater soluble and is doped, wherein the polythiophene is a regio regularpolythiophene having a degree of regioregularity of at least about 90%,and wherein the polythiophene is in acid form.

Embodiment 21

A method for making a composition according to embodiment 1 comprising:reacting a soluble regioregular polythiophene comprising (i) at leastone organic substituent with a sulfonation reagent so that thepolythiophene comprises at least one sulfonated substituent comprisingsulfur bonding directly to the polythiophene backbone.

Embodiment 22

The method according to embodiment 21, wherein the sulfonation reagentis sulfuric acid.

Embodiment 23

The method according to embodiment 21, wherein the sulfonation reagentis a sulfate compound.

Embodiment 24

The method according to embodiment 21, wherein the reacted polythiopheneis doped.

Embodiment 25

The method according to embodiment 21, wherein the reacting results in adegree of sulfonation of at least 10%.

Embodiment 26

The method according to embodiment 21, wherein the reacting results in adegree of sulfonation of at least 50%.

Embodiment 27

The method according to embodiment 21, wherein the reacting results in adegree of sulfonation of at least 75%.

Embodiment 28

The method according to embodiment 21, wherein the sulfonation reagentis sulfuric acid, and the reacting results in a degree of sulfonation ofat least 75%.

Embodiment 29

The method according to embodiment 21, wherein the sulfonation reagentis sulfuric acid, and the reacting results in a degree of sulfonation ofat least 75%, and wherein the polythiophene is a regio regularpolythiophene having a degree of regioregularity of at least about 90%.

Embodiment 30

The method according to embodiment 21, wherein the reacting results in adegree of sulfonation of at least 50%, and wherein the polythiophene isa regio regular polythiophene having a degree of regioregularity of atleast about 98%.

Embodiment 31

A coating composition comprising: (A) water, (B) a water soluble orwater-dispersible regioregular polythiophene comprising (i) at least oneorganic substituent, and (ii) at least one sulfonated substituentcomprising sulfur bonding directly to the polythiophene backbone, (C) asynthetic polymer different from (B).

Embodiment 32

The coating composition according to embodiment 31, further comprisingan organic co-solvent.

Embodiment 33

The coating composition according to embodiment 31, further comprisingan organic co-solvent, wherein the weight amount of water is greaterthan the weight amount of the organic co-solvent.

Embodiment 34

The coating composition according to embodiment 31, further comprising asecond synthetic polymer different from (B) and (C).

Embodiment 35

The coating composition according to embodiment 31, wherein thesynthetic polymer is a water-soluble polymer.

Embodiment 36

The coating composition according to embodiment 31, wherein thesynthetic polymer has a carbon backbone with a polar functional group inthe side group.

Embodiment 37

The coating composition according to embodiment 31, wherein the amountof the synthetic polymer (C) is at least three times the amount of theregioregular polythiophene (B).

Embodiment 38

The coating composition according to embodiment 31, wherein the amountof the synthetic polymer (C) is at least five times the amount of theregioregular polythiophene (B).

Embodiment 39

The coating composition according to embodiment 31, wherein the amountof the regioregular polythiophene polymer (B) is about 5 wt. % to about25 wt. % with respect to the total amount of (B) and (C).

Embodiment 40

The coating composition according to embodiment 31, further comprisingan organic co-solvent, wherein the weight amount of water is greaterthan the weight amount of the organic co-solvent, wherein the amount ofthe synthetic polymer (C) is at least three times the amount of theregioregular polythiophene (B), and wherein the amount of theregioregular polythiophene polymer (B) is about 5 wt. % to about 25 wt.% with respect to the total amount of (B) and (C).

Embodiment 41

A method of making a coating composition comprising: (A) providingwater, (B) providing a water soluble or water-dispersible regioregularpolythiophene comprising (i) at least one organic substituent, and (ii)at least one sulfonated substituent comprising sulfur bonding directlyto the polythiophene backbone, (C) providing a synthetic polymerdifferent from (B), (D) combining in any order (A), (B), and (C) to forma coating composition.

Embodiment 42

A coated substrate comprising: a solid surface, a coating disposed onthe surface, wherein the coating comprises a composition comprising: awater soluble, water dispersible, or water swellable regioregularpolythiophene comprising (i) at least one organic substituent, and (ii)at least one sulfonated substituent comprising sulfur bonding directlyto the polythiophene backbone.

Embodiment 43

A coated substrate comprising: (B) a water soluble, water-dispersible,or water swellable regioregular polythiophene comprising (i) at leastone organic substituent, and (ii) at least one sulfonated substituentcomprising sulfur bonding directly to the polythiophene backbone, (C) asynthetic polymer different from (B).

Embodiment 44

A device comprising a layer comprising the composition according toembodiment 1.

Embodiment 45

The device according to embodiment 44, wherein the layer is a holeinjection layer or a hole transport layer.

Embodiment 46

The device according to embodiment 44, wherein the device is an OLEDdevice.

Embodiment 47

The device according to embodiment 44, wherein the device is a PLEDdevice.

Embodiment 48

The device according to embodiment 44, wherein the device is a SMOLEDdevice.

Embodiment 49

The device according to embodiment 44, wherein the device is aphotovoltaic device.

Embodiment 50

The device according to embodiment 44, wherein the device comprises atleast two electrodes and at least one light emitting or photoactivelayer.

Embodiment 51

A device comprising the composition according to claim 1, wherein thedevice is a sensor, a supercapacitor, a cation transducer, a drugrelease device, an electrochromic device, a transistor, a field effecttransistor, an actuator, or a transparent electrode.

Embodiment 52

A device comprising a hole injection layer or a hole transport layer,the layer comprising a sulfonated conducting polymer.

Embodiment 53

The device according to embodiment 52, wherein the conducting polymer isa heterocyclic conducting polymer.

Embodiment 54

The device according to embodiment 52, wherein the conducting polymer isa polythiophene.

Embodiment 55

The device according to embodiment 52, wherein the conducting polymer isa regioregular polythiophene.

Embodiment 56

A composition comprising: a water soluble or water dispersibleregioregular heterocyclic polymer comprising (i) at least one organicsubstituent, and (ii) at least one sulfonated substituent comprisingsulfur bonding directly to the polymer backbone.

Embodiment 57

A composition comprising: a water soluble, water dispersible, or waterswellable regioregular polythiophene comprising (i) at least one organicsubstituent, and (ii) at least one sulfonated substituent comprisingsulfur bonding directly to the polythiophene backbone.

Embodiment 58

A composition comprising: a water soluble, water dispersible, or waterswellable polythiophene comprising (i) at least one organic substituent,and (ii) at least one sulfonated substituent comprising sulfur bondingdirectly to the polythiophene backbone, wherein the polythiophenebackbone comprises an alternating structure.

Embodiment 59

A composition comprising: a water soluble or water dispersibleregioregular polythiophene comprising (i) at least one organicsubstituent, and (ii) at least one sulfonated substituent comprisingsulfur bonding directly to the polythiophene backbone, wherein theorganic substituent (i) provides the regioregularity apart from thesulfonated substituent (ii).

Embodiment 60

A composition comprising: a water soluble or water dispersibleregioregular polythiophene comprising (i) at least one organicsubstituent, and (ii) at least one sulfonated substituent comprisingsulfur bonding directly to the polythiophene backbone, wherein theregioregular polythiophene comprises regioregular HH-TT or TT-HHpoly(3-substituted thiophene) apart from sulfonation.

Embodiment 61

A device comprising an electrostatic dissipation (ESD) material, saidESD material comprising at least one water soluble or water dispersiblepolymer comprising regioregular polythiophene comprising: (i) at leastone organic substituent; and (ii) at least one sulfonated substituentcomprising sulfur bonding directly to the polythiophene backbone.

Embodiment 62

The device of embodiment 61 wherein the ESD material further comprisesat least one polymer without regioregular polythiophene.

Embodiment 63

The device of embodiment 62 wherein the number average molecular weightof the polymer comprising regioregular polythiophene is about 5,000 toabout 50,000.

Embodiment 64

The device of embodiment 62, wherein at least one polymer iscrosslinked.

Embodiment 65

The device of embodiment 62 wherein the polymer comprising regioregularpolythiophene, and the polymer without regioregular polythiophene form acompatible blend.

Embodiment 66

The device of embodiment 61 wherein the polymer comprising theregioregular polythiophene is a homopolymer.

Embodiment 67

The device of embodiment 61 wherein the polymer comprising theregioregular polythiophene is a copolymer.

Embodiment 68

The device of embodiment 61 wherein the polymer comprising regioregularpolythiophene is a block copolymer, and one segment of the blockcopolymer comprises regioregular polythiophene.

Embodiment 69

The device of embodiment 61 wherein the regioregular polythiophene has adegree of regioregularity of at least 85%.

Embodiment 70

The device of embodiment 61 wherein the regioregular polythiophene has adegree of regioregularity of at least 95%.

Embodiment 71

The device of embodiment 61 wherein the amount of the regioregularpolythiophene in the coating is less than about 50 wt. %.

Embodiment 72

The device of embodiment 61 wherein the amount of the regioregularpolythiophene in the coating is less than about 30 wt. %.

Embodiment 73

The device of to embodiment 61 wherein the polymer which does notcomprise regioregular polythiophene is a synthetic polymer.

Embodiment 74

The device of embodiment 61 or 62 wherein the material is organic,inorganic or ambient doped.

Embodiment 75

The device of embodiment 61 or 62 wherein the regioregular polythiopheneis oxidized.

Embodiment 76

The device of embodiment 61 or 62 wherein the material is doped with Br,I, Cl or any combination thereof.

Embodiment 77

The device of embodiment 61 or 62 wherein the material is doped with:iron trichloride, gold trichloride, arsenic pentafluoride, alkali metalsalts of hypochlorite, protic acids, benzenesulfonic acid andderivatives thereof, propionic acid, organic carboxylic and sulfonicacids, nitrosonium salts, NOPF₆, NOBF₄, organic oxidants,tetracyanoquinone, dichlorodicyanoquinone, hypervalent iodine oxidants,iodosylbenzene, iodobenzene diacetate or a combination thereof.

Embodiment 78

The device of embodiment 61 or 62 wherein the material further comprisesa polymer comprising an oxidative functionality, acidic functionality,poly(styrene sulfonic acid) or a combination thereof.

Embodiment 79

The device of embodiment 61 or 62 wherein the material further comprisesa Lewis acid, iron trichloride, gold trichloride, arsenic pentafluorideor a combination thereof.

Embodiment 80

The device of embodiment 61 or 62 wherein the material further comprisesprotic organic acids, inorganic acids, benzenesulfonic acids andderivatives thereof, propionic acid, organic carboxylic acids, sulfonicacids, mineral acids, nitric acids, sulfuric acids and hydrochloricacids.

Embodiment 81

The device of embodiment 61 or 62 wherein the material further comprisestetracyanoquinone, dichlorodicyanoquinone, hypervalent iodine,iodosylbenzene, iodobenzene diacetate or a combination thereof.

Embodiment 82

The device of embodiment 61 or 62 wherein the material is doped withoxygen, carbon dioxide, moisture, or a combination thereof.

Embodiment 83

The device of embodiment 61 wherein the material is applied via spincoating, ink jetting, roll coating, gravure printing, dip coating, orzone casting.

Embodiment 84

The device of embodiment 61 wherein the material is in a form to havethickness greater than 10 nm.

Embodiment 85

The device of embodiment 61 wherein the polymer comprising regioregularpolythiophene is doped sufficiently to provide the material with anelectronic conductivity of at least about 10⁻¹⁰ siemens/cm.

Embodiment 86

The device of embodiment 61, wherein the electronic conductivity of thematerial is about 10⁻¹³ siemens/cm to about 10⁻³ siemens/cm.

Embodiment 87

The device of embodiment 86 wherein the material is able to retainelectronic conductivity of at least 10⁻¹³ for at least 1000 hrs.

Embodiment 88

The device of embodiment 61, wherein the material is applied to aninsulative surface of said device.

Embodiment 89

The device of embodiment 61, wherein the material is applied to asurface of said device, said surface comprising: glass, silica, polymeror a combination thereof.

Embodiment 90

The device of embodiment 61, wherein the polymer comprising regioregularpolythiophene is doped with an organic dopant and is substituted with aheteroatom.

Embodiment 91

The device of embodiment 61, wherein the regioregular polythiophene isdoped with a quinone compound and the coating has a thickness of about10 nm to about 100 nm, and wherein the polymer which does not compriseregioregular polythiophene comprises a polystyrene, a polystyrenederivative, a polyurethane, a polyacrylate, a polypyridine, or apolyvinyl phenol.

Embodiment 92

The device of embodiment 61, wherein transparency of the material is atleast 90% over the wavelength region of 300 nm to 800 nm.

Embodiment 93

The device of embodiment 61 or 62 wherein the material is doped withsolids, liquids, gases, or a combination thereof.

Embodiment 94

The device of embodiment 61 wherein said device is a component of asemiconductor device, display screen, projector, aircraft wide screen,vehicular wide screen or CRT screens.

Embodiment 95

The device according to embodiment 61, wherein the material is a coatingor packaging material.

Embodiment 96

A method of reducing electrostatic charge on a device comprising coatingsaid device with a coating comprising a polythiophene comprising: (i) atleast one organic substituent; and (ii) at least one sulfonatedsubstituent comprising sulfur bonding directly to the polythiophenebackbone.

Embodiment 97

The method of embodiment 96, wherein said coating further comprises atleast one polymer which does not comprise polythiophene.

Various terms are further described hereinbelow:

“Alkyl” can be for example straight chain and branched monovalent alkylgroups having from 1 to 20 carbon atoms, or from 1 to 15 carbon atoms,or from 1 to 10, or from 1 to 5, or from 1 to 3 carbon atoms. This termis exemplified by groups such as for example methyl, ethyl, n-propyl,iso-propyl, n-butyl, t-butyl, n-pentyl, ethylhexyl, dodecyl, isopentyl,and the like.

“Optionally substituted” groups can be for example functional groupsthat may be substituted or unsubstituted by additional functionalgroups. For example, when a group is unsubstituted by an additionalgroup it can be referred to as the group name, for example alkyl oraryl. When a group is substituted with additional functional groups itmay more generically be referred to as substituted alkyl or substitutedaryl.

“Substituted alkyl” can be for example an alkyl group having from 1 to3, and preferably 1 to 2, substituents selected from the groupconsisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy,aryl, substituted aryl, aryloxy, substituted aryloxy, hydroxyl.

“Aryl” can be for example a monovalent aromatic carbocyclic group offrom 6 to 14 carbon atoms having a single ring (e.g., phenyl) ormultiple condensed rings (e.g., naphthyl or anthryl) which condensedrings may or may not be aromatic provided that the point of attachmentis at an aromatic carbon atom. Preferred aryls include phenyl, naphthyl,and the like.

“Substituted aryl” can be for example to an aryl group with from 1 to 5substituents, or optionally from 1 to 3 substituents, or optionally from1 to 2 substituents, selected from the group consisting of hydroxy,alkyl, substituted alkyl, alkoxy, substituted alkoxy, alkenyl,substituted alkenyl, substituted aryl, aryloxy, substituted aryloxy, andsulfonate

“Alkoxy” can be for example the group “alkyl-O—” which includes, by wayof example, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy,t-butyloxy, n-pentyloxy, 1-ethylhex-1-yloxy, dodecyloxy, isopentyloxy,and the like.

“Substituted alkoxy” can be for example the group “substitutedalkyl-O—.”

“alkylene” can be for example straight chain and branched divalent alkylgroups having from 1 to 20 carbon atoms, or from 1 to 15 carbon atoms,or from 1 to 10, or from 1 to 5, or from 1 to 3 carbon atoms. This termis exemplified by groups such as methylene, ethylene, n-propylene,iso-propylene, n-butylene, t-butylene, n-pentylene, ethylhexylene,dodecylene, isopentylene, and the like.

“Alkenyl” can be for example an alkenyl group preferably having from 2to 6 carbon atoms and more preferably 2 to 4 carbon atoms and having atleast 1 and preferably from 1-2 sites of alkenyl unsaturation. Suchgroups are exemplified by vinyl, allyl, but-3-en-1-yl, and the like.

“Substituted alkenyl” can be for example alkenyl groups having from 1 to3 substituents, and preferably 1 to 2 substituents, selected from thegroup consisting of alkoxy, substituted alkoxy, acyl, acylamino,acyloxy, amino, substituted amino, aminoacyl, aryl, substituted aryl,aryloxy, substituted aryloxy, cyano, halogen, hydroxyl, nitro, carboxyl,carboxyl esters, cycloalkyl, substituted cycloalkyl, heteroaryl,substituted heteroaryl, heterocyclic, and substituted heterocyclic withthe proviso that any hydroxyl substitution is not attached to a vinyl(unsaturated) carbon atom.

“Aryloxy” can be for example the group aryl-O— that includes, by way ofexample, phenoxy, naphthoxy, and the like.

“Substituted aryloxy” can be for example substituted aryl-O— groups.

“Alkylene oxide” can be for example the group —(R^(a)—O)_(n)—R^(b) whereR^(a) is alkylene and R^(b) is alkyl or optionally substituted aryl andn is an integer from 1 to 6, or from 1 to 3. Alkylene oxide can be forexample groups based on such as groups as ethylene oxides or propyleneoxides.

“salt” can be for example derived from a variety of organic andinorganic counter ions well known in the art and include, by way ofexample only, sodium, potassium, calcium, magnesium, ammonium,tetraalkylammonium, and the like; and when the molecule contains a basicfunctionality, salts of organic or inorganic acids, such ashydrochloride, hydrobromide, tartrate, mesylate, acetate, maleate,oxalate and the like.

In substituted groups described above, polymers arrived at by describingsubstituents with further substituents to themselves (e.g., substitutedaryl having a substituted aryl group as a substituent which is itselfsubstituted with a substituted aryl group, etc.) are not intended forinclusion herein. In such cases, the maximum number of such substituentsis three. That is to say that each of the above descriptions can beconstrained by a limitation that, for example, substituted aryl groupsare limited to—substituted aryl-(substituted aryl)-substituted aryl.

Similarly, the above descriptions are not intended to includeimpermissible substitution patterns (e.g., methyl substituted with 5fluoro groups or a hydroxyl group alpha to ethenylic or acetylenicunsaturation). Such impermissible substitution patterns are well knownto the skilled artisan.

All references described herein are hereby incorporated by reference intheir entirety.

One skilled in the art can employ the following references in thepractice of the various embodiments described herein. In particular,several references describe conducting polymers, polythiophenes,regioregular polythiophenes, substituted polythiophenes, and OLED, PLED,and PV devices prepared from them, and these can be used in the practiceof one or more of the present embodiments. In reciting a conductingpolymer name, the name can also include derivatives thereof. Forexample, polythiophene can include polythiophene derivatives.

Electrically conductive polymers are described in The Encyclopedia ofPolymer Science and Engineering, Wiley, 1990, pages 298-300, includingpolyacetylene, poly(p-phenylene), poly(p-phenylene sulfide),polypyrrole, and polythiophene, which is hereby incorporated byreference in its entirety. This reference also describes blending andcopolymerization of polymers, including block copolymer formation.

In addition, provisional patent application Ser. No. 60/612,640 filedSep. 24, 2004 to Williams et al. (“HETEROATOMIC REGIOREGULARPOLY(3-SUBSTITUTEDTHIOPHENES) FOR ELECTROLUMINESCENT DEVICES”) and U.S.regular application Ser. No. 11/234,374 filed Sep. 26, 2005 are herebyincorporated by reference in their entirety including the description ofthe polymers, the figures, and the claims.

Provisional patent application Ser. No. 60/612,641 filed Sep. 24, 2004to Williams et al. (“HETEROATOMIC REGIOREGULAR POLY(3-SUBSTITUTEDTHIOPHENES) FOR PHOTOVOLTAIC CELLS”) and U.S. regularapplication Ser. No. 11/234,373 filed Sep. 26, 2005 are herebyincorporated by reference in their entirety including the description ofthe polymers, the figures, and the claims.

The U.S. regular application Ser. No. 11/350,271, to Williams et al, canbe also used to practice the various embodiments described herein forhole injection and transport layers (“HOLE INJECTION/TRANSPORT LAYERCOMPOSITIONS AND DEVICES”). Another reference which can be used isWilliams et al, Ser. No. 11/376,550, COPOLYMERS OF SOLUBLE POLYTHIOPHENEWITH IMPROVED ELECTRONIC PERFORMANCE, filed Mar. 16, 2006.

Polythiophenes can be homopolymers, copolymers, or block copolymers.Synthetic methods, doping, and polymer characterization, includingregioregular polythiophenes with side groups, is provided in, forexample, U.S. Pat. Nos. 6,602,974 to McCullough et al. and 6,166,172 toMcCullough et al., which are hereby incorporated by reference in theirentirety. Additional description can be found in the article, “TheChemistry of Conducting Polythiophenes,” by Richard D. McCullough, Adv.Mater. 1998, 10, No. 2, pages 93-116, and references cited therein,which is hereby incorporated by reference in its entirety. Anotherreference which one skilled in the art can use is the Handbook ofConducting Polymers, 2^(nd) Ed. 1998, Chapter 9, by McCullough et al.,“Regioregular, Head-to-Tail Coupled Poly(3-alkylthiophene) and itsDerivatives,” pages 225-258, which is hereby incorporated by referencein its entirety. This reference also describes, in chapter 29,“Electroluminescence in Conjugated Polymers” at pages 823-846, which ishereby incorporated by reference in its entirety.

Polythiophenes are described, for example, in Roncali, J., Chem. Rev.1992, 92, 711; Schopf et al., Polythiophenes: Electrically ConductivePolymers, Springer: Berlin, 1997. See also for example U.S. Pat. Nos.4,737,557 and 4,909,959.

Polymeric semiconductors are described in, for example, “OrganicTransistor Semiconductors” by Katz et al., Accounts of ChemicalResearch, vol. 34, no. 5, 2001, page 359 including pages 365-367, whichis hereby incorporated by reference in its entirety.

Block copolymers are described in, for example, Block Copolymers,Overview and Critical Survey, by Noshay and McGrath, Academic Press,1977. For example, this text describes A-B diblock copolymers (chapter5), A-B-A triblock copolymers (chapter 6), and -(AB)_(n)-multiblockcopolymers (chapter 7), which can form the basis of block copolymertypes in the present invention.

Additional block copolymers including polythiophenes are described in,for example, Francois et al., Synth. Met. 1995, 69, 463-466, which isincorporated by reference in its entirety; Yang et al., Macromolecules1993, 26, 1188-1190; Widawski et al., Nature (London), vol. 369, Jun. 2,1994, 387-389; Jenekhe et al., Science, 279, Mar. 20, 1998, 1903-1907;Wang et al., J. Am. Chem. Soc. 2000, 122, 6855-6861; Li et al.,Macromolecules 1999, 32, 3034-3044; Hempenius et al., J. Am. Chem. Soc.1998, 120, 2798-2804;

The following article describes several types of regioregular systemsbeginning at page 97 and references cited therein: “The Chemistry ofConducting Polythiophenes,” by Richard D. McCullough, Adv. Mater. 1998,10, No. 2, pages 93-116. In a regioregular polymer, including apolythiophene, the degree of regioregularity can be, for example, about90% or more, or about 95% or more, or about 98% or more, or about 99% ormore. Methods known in the art such as, for example, NMR can be used tomeasure the degree of regioregularity. Regioregularity can arise inmultiple ways. For example, it can arise from polymerization ofasymmetric monomers such as a 3-alkylthiophene to provide head-to-tail(HT) poly(3-substituted)thiophene. Alternatively, it can arise frompolymerization of monomers which have a plane of symmetry between twoportions of monomer such as for example a bi-thiophene, providing forexample regioregular HH-TT and TT-HH poly(3-substituted thiophenes).

In particular, substituents which can be used to solubilize conductingpolymers with side chains include alkoxy and alkyl including for exampleC1 to C25 groups, as well as heteroatom systems which include forexample oxygen and nitrogen. In particular, substituents having at leastthree carbon atoms, or at least five carbon atoms can be used. Mixedsubstituents can be used. The substituents can be nonpolar, polar orfunctional organic substitutents. The side group can be called asubstituent R which can be for example alkyl, perhaloalkyl, vinyl,acetylenic, alkoxy, aryloxy, vinyloxy, thioalkyl, thioaryl, ketyl,thioketyl, and optionally can be substituted with atoms other thanhydrogen.

Thiophene polymers can be star shaped polymers with the number ofbranches being for example more than three and comprising thiopheneunits. Thiophene polymers can be dendrimers. See for example Anthopouloset al., Applied Physics Letters, 82, 26, Jun. 30, 2003, 4824-4826, andfurther description of dendrimers hereinafter.

Heterocyclic polymers are particularly preferred. A particularlypreferred system is the polythiophene system and the regioregularpolythiophene system. Polymers can be obtained from Plextronics, Inc.,Pittsburgh, Pa. including for example polythiophene-based polymers suchas for example Plexcore, Plexcoat, and similar materials.

Another embodiment includes heterocyclic conjugated polymers which arerelatively regioirregular. For example, the degree of regioregularitycan be about 90% or less, or about 80% or less, or about 70% or less, orabout 60% or less, or about 50% or less.

Sulfonation and Sulfonated Polymers

The aforementioned polymers can be subjected to sulfonation. FIG. 1illustrates a general sulfonation scheme for different conductingpolymers and heterocyclic types of conducting polymers, including thosewhich have a heterocyclic atom such as S, N, Se, Te, and Si. R is notparticularly limited but can be for example a group which provides asolubilizing function such as alkyl or alkoxy.

FIG. 2 illustrates a polythiophene system. For example, some embodimentsprovide a composition comprising: a water soluble or water dispersibleregioregular polythiophene comprising (i) at least one organicsubstituent, and (ii) at least one sulfonated substituent comprisingsulfur bonding directly to the polythiophene backbone.

When a regioregular polymer is subjected to sulfonation, the polymercomposition can be yet called regioregular for present purposes.

Sulfonation is generally known in the art, wherein there is anintroduction into an organic molecule of the sulfonic acid group or itssalts, —SO₃H, wherein the sulfur atom is bonded to carbon of the organicmolecule. Examples in the patent literature include for example U.S.Pat. No. 5,548,060 to Allcock et al.; U.S. Pat. No. 6,365,294 toPintauro et al.; U.S. Pat. No. 5,137,991 to Epstein et al.; and U.S.Pat. No. 5,993,694 to Ito et al. Additional sulfonation methods aredescribed in for example (1) Sotzing, G. A. Substitutedthieno[3,4-b]thiophene polymers, method of making and use thereof,US2005/0124784 A1; (2) Lee, B.; Seshadri, V.; Sotzing, G. A. RingSulfonated poly(thieno[3,4-b]thiophene), Adv. Mater. 2005, 17, 1792.

The sulfonated substituent can be in various forms. For example, thesulfonated substituent can be in acid form; or the sulfonatedsubstituent can be in salt form comprising a counterion; or thesulfonated substituent can be in salt form comprising a counterion,wherein the counterion comprises organic groups; or the sulfonatedsubstituent can be in salt form comprising a counterion, wherein thecounterion comprises an organic cation including for example alkylgroups and is free of metal; or the sulfonated substituent is in saltform comprising a counterion, wherein the counterion comprises a metalcation.

Sulfonation of polymers can be carried out by methods known in the artusing sulfonation reagents. In many cases, it is desirable to reduce theamounts of sulfonating agent needed and the amount of solvent needed. Inmany cases, it is desirable to reduce the amount of work-up neededincluding the amount of work-up solvent such as water to remove forexample excess acid. Sulfonation is represented in FIGS. 1 and 2 forconducting polymers generally and for polythiophenes in particular.Solid polymer can be added to sulfonation reagent in film or powderform. Specialized processes can be used as needed such asmicro-fluidizer or ultrafiltration including use of ultrafiltrationmembrane filters and use of continuous processes.

For example, polythiophene can be treated with fuming sulfuric acid attemperatures of for example about 0 to about 100 degrees celsius, orabout 22 to about 100 degrees celsius, or about 50 to about 100 degreescelsius, or about 80-85 degrees celsius.

The degree of sulfonation can be controlled to for example about 5% toabout 95%, or about 10% to about 90%, or to about 25% to about 75%. Assulfonation progresses, the sulfonated polythiophene is solublizedand/or dispersed in the strong acid.

If desired, the polymers can be treated with ion exchange resins ortreated by ultrafiltration.

After sulfonation, the sulfonated polymer can be modified as illustratedin for example FIG. 3. A variety of bases can be used; exchange of avariety of counterions can be used. This can result in for example (i)neutralizing acid, and/or (ii) tuning the energy levels and altering ofhole injection ability. FIG. 3 illustrates for example metal ion,ammonium ion (including alky and aryl substituted), phosphonium ion(also alkyl or aryl substituted), imidazolinium, thiazolinium, andoxazolinium. Modification can also provide better solubility includingfor example better solubility in organic solvents such as for exampleaprotic solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidinone (NMP), dimethylsulfoxide (DMSO),and the like. Another example of modification is conversion of sulfonicacid to an alkyl/aryl sulfonate ester which could be furthersubstituted. Polymers can be dedoped by addition of a variety of formsof appropriate base in appropriate quantities. In some cases, this canbe observed from blue shifting of the absorption of the conjugatedpolymer.

The type of polymer to be sulfonated can be varied as illustrated in forexample FIG. 4 for a bis-thiophene monomer. Dimers can be used in makingpolymers. Symmetrical dimers can be used. Examples include those whichare HH or TT (head to head, tail to tail, respectively) coupled but haveat least one position open for sulfonation.

In a preferred embodiment, the polymer provides one position forsulfonation.

The polymer microstructure and regioregularity can provide polymerswherein alternating donors and acceptors can be made.

Sulfonation can be performed on the neutral conjugated polymer.

Absorption spectra can be used to confirm that the polymer isself-doped. For example, absorption can extend into the near IR.

The polymers can be very stable in the self-doped state as illustratedin FIG. 5. The properties of the polymer can be controlled by pH andacid content as illustrated in FIG. 6 for pH. Raising pH is aparticularly important formulation strategy. Titration andneutralization can be carried out. Examples of acid content include atleast 10 mg NaOH/g solids, or at least 50 mg NaOH/g solids, at least 100mg NaOH/g solids, or at least 200 mg NaOH/g solids including for example10 mg NaOH/g solids to about 250 mg NaOH/g solids. pH values can be forexample 1.8 to 3.0, or 1.9 to 5, or 2.0 to 7.0. In many cases, it isdesirable to be less acidic than the PEDOT/PSS material. pH can varywith the percentage of solids.

The direct bonding of the sulfonate sulfur atom to the polythiophene canprovide tunability of band gap structure.

In many cases, good dispersibility is desired. Both water soluble andwater dispersible polymers can be used and in many instances it may notbe that important for performance whether the polymer forms a truesolution.

Preferred embodiments include for example the polythiophene is a regioregular polythiophene having a degree of regioregularity of at leastabout 90%; the polythiophene is a regio regular polythiophene having adegree of regioregularity of at least about 98%; the polythiophene iswater soluble; the polythiophene is doped; the organic substitutentcomprises at least one heteroatom; the organic substitutent is an alkoxyor alkyl substituent; the polythiophene is an alternating copolymer; thepolythiophene is prepared from a bithiophene monomer; wherein thepolythiophene is a homopolymer of a thiophene, a copolymer comprisingthiophene units, or a block copolymer comprising at least one block ofpolythiophene; the polythiophene is characterized by a degree ofsulfonation of about 10% to about 90%; the polythiophene ischaracterized by a degree of sulfonation of about 50% to about 90%; thepolythiophene is water soluble, the polythiophene is a homopolymer, andwherein the organic substitutent is an alkoxy or alkyl substituent; thepolythiophene is water soluble, and wherein the polythiophene is in saltform comprising a counterion, wherein the counterion comprises organicgroups; and the polythiophene is water soluble and is doped, wherein thepolythiophene is a regio regular polythiophene having a degree ofregioregularity of at least about 90%, and wherein the polythiophene isin acid form. The water soluble or water dispersible polythiophene canbe in crosslinked form so it is water swellable.

The polymer can be converted to film form by methods known in the artfor characterization of for example UV-Vis-NIR properties andelectrochemistry for the tuning of energy levels including HOMO andLUMO. Stability can be examined.

In some embodiments, sulfonation may also result in substitutent or sidegroups also comprising sulfonate groups. For example, an aromatic orphenyl group in the substituent could be sulfonated.

Additional Embodiments for Polymer

In addition, an embodiment for the polymer which can be subjected tosulfonation to produce sulfonated substituents on the polymer backbonecan be represented by formula (I),

wherein R can be optionally substituted alkyl, optionally substitutedalkoxy, and optionally substituted aryloxy. Examples of substituents forthe optional substitution include hydroxyl, phenyl, and additionaloptionally substituted alkoxy groups. The alkoxy groups can be in turnoptionally substituted with hydroxyl, phenyl, or alkoxy groups; or

wherein R can be an optionally substituted alkylene oxide. Substituentscan be for example hydroxyl, phenyl, or alkoxy groups; or

wherein R can be optionally substituted ethylene oxide or optionallysubstituted propylene oxide or other lower alkyleneoxy units.Substituents can be for example hydroxyl, phenyl, or alkoxy groups; or

R can be an optionally substituted alkylene such as for examplemethylene or ethylene, with substituents being for example optionallysubstituted alkyleneoxy such as ethyleneoxy or propyleneoxy;substituents can be for example hydroxyl, phenyl, or alkoxy.

Examples of I are shown in FIG. 15.

In addition, the substitutent group R in (I) can be linked to thethiophene by an oxygen atom as alkoxy or phenoxy, wherein thesubstituent can be characterized by the corresponding alcohol or phenol,respectively. The alcohol, for example, can be linear or branched, andcan have C2-C20, or C4-C18, or C6 to C14 carbon atoms. The alcohol canbe for example an alkyl alcohol, or an ethylene glycol, or a propyleneglycol, or a diethylene glycol, or a dipropylene glycol, or atripropylene glycol. Additional examples can be monoethylene glycolethers and acetates, diethylene glycol ethers and acetates, triethyleneglycol ethers and acetates, and the like. Examples of alcohols which canbe linked to the thiophene ring through the oxygen atom include hexylcellosolve, Dowanol PnB, ethyl carbitol, Dowanol DPnB, phenyl carbitol,butyl cellosolve, butyl carbitol, Dowanol DPM, diisobutyl carbinol,2-ethylhexyl alcohol, methyl isobutyl carbinol, Dowanol Eph, DowanolPnP, Dowanol PPh, propyl carbitol, hexyl carbitol, 2-ethylhexylcarbitol, Dowanol DPnP, Dowanol TPM, methyl carbitol, Dowanol TPnB.Trade names are well known in this art. See for example DOW P-series andE-series glycol ethers.

The structure shown in (I) can stand alone as a polymer or it can bepart of a block copolymer with another segment.

In FIG. 15, the n value for the polymers Ia, Ib, Ic, and Id can reflectmolecular weights known in the art and in references cited herein suchas for example, 25-5,000, or 50-1,000;

In FIG. 15, the p value for Ia-Id can be for example 0, 1, or 2.

In FIG. 15, for the polymers Ia, Ib, Ic, and Id, the m value can be forexample 0, 1, 2, 3, or 4, or even higher such as for example 6, 11, or16 (e.g., as found in Carbowax PEG 350, 550, 750).

In FIG. 15, for the polymers Ia, Ib, Ic, and Id, Y can be for examplehydrogen, C1-C8 alkyl, optionally substituted C1-C6 alkenyl, and aryl.In addition, Y can be for example hydrogen, optionally substitutedvinyl, optionally substituted allyl, methyl, ethyl, propyl, butyl,hexyl, octyl, or phenyl. Alternatively, Y can be for example hydrogen,methyl, ethyl, prop-1-yl, hex-1-yl, hex-2-yl, hex-3-yl, oct-1-yl,oct-2-yl, oct-3-yl, oct-4-yl.

In FIG. 15, for the polymers Ia, Ib, Ic, and Id, R1 and R2 independentlycan be selected from hydrogen and methyl, provided that only one of R1and R2 is methyl. R1 and R2 can be each hydrogen. R1 can be methyl andR2 can be hydrogen. R1 can be hydrogen and R2 can be methyl.

Methods of Making Sulfonated Polymers

Described herein also are methods of making compositions and methods ofusing compositions. For example, one embodiment provides a method formaking a composition according to claim 1 comprising: reacting a solubleregioregular polythiophene comprising at least one organic substituentwith a sulfonation reagent so that the polythiophene comprises at leastone sulfonated substituent comprising sulfur bonding directly to thepolythiophene backbone. In preferred embodiments, the sulfonationreagent is sulfuric acid; the sulfonation reagent is a sulfate compound;the reacted polythiophene is doped; the reacting results in a degree ofsulfonation of at least 10%; the reacting results in a degree ofsulfonation of at least 50%; the reacting results in a degree ofsulfonation of at least 75%; the sulfonation reagent is sulfuric acid,and the reacting results in a degree of sulfonation of at least 75%; thesulfonation reagent is sulfuric acid, and the reacting results in adegree of sulfonation of at least 75%, and wherein the polythiophene isa regio regular polythiophene having a degree of regioregularity of atleast about 90%; and the reacting results in a degree of sulfonation ofat least 50%, and wherein the polythiophene is a regio regularpolythiophene having a degree of regioregularity of at least about 98%.

The degree of sulfonation can be for example about 10% to about 100%, orabout 30% to about 90%, or about 50% to 90%.

The acid value or acid number (mg KOH/g polymer) can be adapted for anapplication but can be for example about 250 mg KOH/g polymer, or about50 to about 250 mg KOH/g polymer, or about 75 to about 200 mg KOH/gpolymer, or about 100 to about 150 mg KOH/g polymer. This can be lessthan competitive polymers such as for example CH8000 which has 651 mgKOH/g solid. A solution formulated for, for example, an HIL applicationcan have an acid value of for example about 0.1 to about 0.8 mg KOH/gHIL solution, or about 0.2 mg to about 0.6 mg KOH/g HIL solution.

The pH of the formulation can be for example greater than about 2, orabout 2.0 to about 3.0, or about 2.3 to about 2.7. This can be lessacidic than a variety of competitive materials such as for exampleBaytron AI4083 which exhibits a pH of about 1.7 and CH8000 whichexhibits a pH of about 1.3.

Formulation and Blending

The conducting polymer and polythiophene compositions, sulfonated asdescribed above, can be formulated and blended by methods known in theart to formulators including, for example, varying the amounts of thecomponents, varying combinations of different structural types, use ofdifferent mixing conditions, using different solvents, applyingdifferent film preparation conditions, using different purificationmethods, and the like. Formulations for specific applications in holeinjection technology are particularly important.

The blend can be compatible when it is not characterized by excessivephase separation and forms functionally useful, mechanically stablefilms which can function as a hole injection layer. Compatible blendsare known in the art. See, for example, U.S. Pat. Nos. 4,387,187;4,415,706; 4,485,031; 4,898,912; 4,929,388; 4,935,164; and 4,990,557.Compatible blends do not have to be miscible blends, but aresufficiently mixed and stable to provide useful function, particularlyin thin film form such as, for example, about 2 nm to about 100 nm.Blending methods may include solution blending of a predissolvedconducting polymer either in neutral or oxidized form disintegrated intonanosized particles (typically from tens to hundreds of nanometers) withconventional polymers (e.g., polystyrene (PS), poly(methyl methacrylate)(PMMA), poly(vinyl acetate) (PVA)) by sonicating, agitation, or shear.Such blends provide fine dispersion of film-forming submicronicparticles of stable polymer matrix solutions. Films can be prepared andanalyzed for compatibility by spin coating.

In this invention, a matrix component can be used which helps providethe needed properties, such as planarization, for the hole injection orhole transport layers. The matrix component, including planarizingagents, when blended with the hole injection component, will facilitatethe formation of the HIL or HTL layer in a device such as an OLED or PVdevice. It will also be soluble in the solvent that is used to apply theHIL system. The planarizing agent may be comprised of, for example, apolymer or oligomer such as an organic polymer such as poly(styrene) orpoly(styrene) derivatives, poly(vinyl acetate) or its derivatives,poly(ethylene glycol) or its derivatives, poly(ethylene-co-vinylacetate), poly(pyrrolidone) or its derivatives (e.g.,poly(1-vinylpyrrolidone-co-vinyl acetate)), poly(vinyl pyridine) or itsderivatives, poly(methyl methacrylate) or its derivatives, poly(butylacrylate) or its derivatives. More generally, it can be comprised ofpolymers or oligomers built from monomers such as CH₂CH Ar, where Ar=anyaryl or functionalized aryl group, isocyanates, ethylene oxides,conjugated dienes, CH₂CHR₁R (where R₁=alkyl, aryl, or alkyl/arylfunctionalities and R=H, alkyl, Cl, Br, F, OH, ester, acid, or ether),lactam, lactone, siloxanes, and ATRP macroinitiators.

More than one non-conductive polymer can be used in the formulation.

In this invention, the planarizing agent and the hole injectioncomponent could be represented by a copolymer that contains an ICPsegment and a non-conjugated segment with a composition like similar tothat described herein.

In this invention, the planarizing agent can also be a “non-fugitive”,small molecule that is soluble in the application solvent, but does notevaporate upon removal of the solvent. It may possess alkyl, aryl, orfunctional alkyl or aryl character.

In addition to facilitating the providing of a smooth surface to the HILlayer, the matrix component or planarization agent can also provideother useful functions such as resistivity control and transparencycontrol. Planarity can be determined by methods known in the artincluding AFM measurements.

The solvent system, or solvents for dispersing polymers, can be amixture of water and organic solvent, including water miscible solvents,and solvents that comprise oxygen, carbon, and hydrogen, such as forexample an alcohol or an etheric alcohol. Additional examples of watermiscible solvents include alcohols such as isopropanol, ethanol, andmethanol, and ethylene glycols and propylene glycols from Dow Chemicaland Eastman Chemical. See for example Cellosolve, Carbitol, propanediol, methyl carbitol, butyl cellosolve, Dowanol PM, In someembodiments, the amount of water can be greater than the amount oforganic solvent. A wide variety of combination of solvents can be usedincluding non-aqueous including alcohols and other polar solvents. Thecomposition can comprise a first solvent and a second solvent, differentthan the first solvent.

In particular, water soluble resins and aqueous dispersions can be used.Aqueous dispersions can be for example poly(styrene sulfonic acid) (i.e.PSS dispersion), Nafion dispersion (e.g., sulfonated fluorinatedpolymers), latex, and polyurethane dispersions. Examples of watersoluble polymers include polyvinylpyrollidinone and polyvinylalcohol.Other examples of resins include cellulose acetate resins (CA, CAB,CAP—Eastman).

Formulation can be carried out to modify surface energy, conductivity,film formation, solubility, crosslinking, morphology, film quality,specific application (e.g, spin coat, ink jet printing, screen printing,and the like).

Surfactants can be used including for example ionic and non-ionicsurfactants, as well as polymer surfactants, fluorinated surfactants,and ionomers.

Resins and HIL inks can be dispersed and/or dissolved by any methodknown in the art including for example sonication.

If desired, the formulation can be formulated to include crosslinkingagents which provide crosslinked structures which may swell but notdissolve upon crosslinking.

Preferred embodiments include for example a coating compositioncomprising: (A) water, (B) a water soluble or water-dispersibleregioregular polythiophene comprising (i) at least one organicsubstituent, and (ii) at least one sulfonated substituent comprisingsulfur bonding directly to the polythiophene backbone, and (C) asynthetic polymer different from (B); optionally further comprising anorganic co-solvent; or further comprising an organic co-solvent, whereinthe weight amount of water is greater than the weight amount of theorganic co-solvent; or further comprising a second synthetic polymerdifferent from (B) and (C); wherein the synthetic polymer is awater-soluble polymer; or wherein the synthetic polymer has a carbonbackbone with a polar functional group in the side group; or wherein theamount of the synthetic polymer (C) is at least three times the amountof the regioregular polythiophene (B); wherein the amount of thesynthetic polymer (C) is at least five times the amount of theregioregular polythiophene (B); or wherein the amount of theregioregular polythiophene polymer (B) is about 5 wt. % to about 25 wt.% with respect to the total amount of (B) and (C); or, and furthercomprising an organic co-solvent, wherein the weight amount of water isgreater than the weight amount of the organic co-solvent, wherein theamount of the synthetic polymer (C) is at least three times the amountof the regioregular polythiophene (B), and wherein the amount of theregioregular polythiophene polymer (B) is about 5 wt. % to about 25 wt.% with respect to the total amount of (B) and (C).

Additional embodiments for materials and polymers that can be added tothe formulation include, for example, poly(vinyl alcohol), includingpoly(vinyl alcohol) which is 88% hydrolyzed,poly(2-acrylamido-2-methyl-1-propane sulfonic acid),poly(2-acrylamido-2-methyl-1-propane sulfonic acid-co-styrene),poly(1-vinyl pyrolidone-co-vinyl acetate), poly(acrylamide-co-acrylicacid), polyurethane dispersion, acrylic latex dispersion,poly(styrene-ran-ethylene)sulfonated solution, poly(4-vinylphenol)-co-PMMA, poly(vinyl acetate-co-butyl maleate-co-isobornylacrylate), poly-4-vinylpyridine, and combinations thereof. In somecases, the poly-4-vinylpyridine may not provide as good results as othermaterials.

In another embodiment, the sulfonated polymer is dissolved or dispersedin water, or a mixture of water and a water soluble organic solvent, oran organic solvent. Optionally, additional ingredients can be mixed inincluding for example a second type of polymer.

The compositions can comprise a first solvent and a second solvent. Forexample, the first solvent can be water and the second solvent can be anorganic solvent miscible with water. These two solvents can be mixed ina wide variety of ratios adapted for a particular application. In somecases, one can eliminate or substantially eliminate the first solvent,or eliminate or substantially eliminate the second solvent. The relativeamount (by weight or volume) of the first solvent to second solvent canrange from for example 100 parts first solvent and 0 parts secondsolvent, to 0 parts first solvent and 100 parts second solvent, or 90parts first solvent and 10 parts second solvent, to 10 parts firstsolvent and 90 parts second solvent, 80 parts first solvent and 20 partssecond solvent, to 20 parts first solvent and 80 parts second solvent,30 parts first solvent and 70 parts second solvent, to 70 parts firstsolvent and 30 parts second solvent, 60 parts first solvent and 40 partssecond solvent, to 40 parts first solvent and 60 parts second solvent.

For many formulations, the amount of sulfonated polymer is at leastabout 4 wt. % with respect to the solid content

For some embodiment, the sulfonated polymer can be present with respectto total solid content at about 1 wt. % to about 10 wt. %, or about 4wt. % to about 8 wt. %.

Coated Substrates

Also provided is a coated substrate comprising: a solid surface, acoating disposed on the surface, wherein the coating comprises acomposition comprising: a water soluble, water dispersible, or waterswellable regioregular polythiophene comprising (i) at least one organicsubstituent, and (ii) at least one sulfonated substituent comprisingsulfur bonding directly to the polythiophene backbone. Surfaces usefulin OLED and OPV applications can be used. For example, the solid surfacecan be for example an electrode including a transparent electrode suchas indium tin oxide. The surface can be a light emitting polymer layeror a hole transport layer. The thickness of the coating can be forexample 5 nm to 5 microns, 10 nm to 1 micron, 25 nm to 500 nm, or 50 nmto 250 nm. Residual solvent may be present. The coating may becrosslinked or patterned.

Also provided is a coated substrate comprising: (A) a solid surfacehaving a coating disposed thereon comprising (B) a water soluble orwater-dispersible regioregular polythiophene comprising (i) at least oneorganic substituent, and (ii) at least one sulfonated substituentcomprising sulfur bonding directly to the polythiophene backbone, and(C) a synthetic polymer different from (B). Surfaces useful in OLED andOPV applications can be used. For example, the solid surface can be forexample an electrode including a transparent electrode such as indiumtin oxide. The surface can be a light emitting polymer layer or a holetransport layer. The thickness of the coating can be for example 5 nm to5 microns, 10 nm to 1 micron, 25 nm to 500 nm, or 50 nm to 250 nm.Residual solvent may be present. The coating may be crosslinked orpatterned.

Any coating or patterning method known in the art can be used.Microscale or nanoscale patterning can be carried out to formnanostructure or microstructures on the surface.

Printing processes can include for example flexography, letter press,soft lithography, gravure, pad, offset lithography, screen, and inkjetprinting.

The surface can be the surface of a homogeneous, heterogeneous, ormultilayer substrate.

Substrates can be those used in printed electronics. Substrates can befor example plastic, glass, metals, including silver and gold.

Films and Coatings and Properties

In this invention, the HIL system is preferred and can be applied byspin casting, drop casting, dip-coating, spray-coating, or by printingmethods such as ink jet printing, off-set printing, or by a transferprocess. For example, ink jet printing is described in U.S. Pat. No.6,682,175 to Otsuka and in Hebner et al., Applied Physics Letters, 72,no. 5, Feb. 2, 1998, pages 519-521.

In this invention, an HIL as a film of an HIL system can be providedthat is about 10 nm to about 50 μm in thickness with typical thicknessranging from about 50 nm to about 1 μM. In another embodiment, thicknesscan be about 10 nm to about 500 nm, and more particularly, about 10 nmto about 100 nm.

Good surface smoothness and interfacial properties are important.

Device Fabrication and Testing

Various devices can be fabricated in many cases using multilayeredstructures which can be prepared by for example solution or vacuumprocessing, as well as printing and patterning processes. In particular,use of the embodiments described herein for hole injection and holetransport can be carried out effectively (HILs and HTLs for HoleInjection Layers, and Hole Transport Layers, respectively). Inparticular, applications include hole injection layer for OLEDs, PLEDs,photovoltaic cells, supercapacitors, cation transducers, drug release,electrochromics, sensors, FETs, actuators, and membranes. Anotherapplication is as an electrode modifier including an electrode modifierfor an organic field effect transistor (OFETS). Other applicationsinclude those in the field of printed electronics, printed electronicsdevices, and roll-to-roll production processes.

For example, photovoltaic devices are known in the art as illustrated infor example FIG. 7. The devices can comprise, for example, multi-layerstructures including for example an anode such as ITO on glass or PET; ahole injection layer; a P/N bulk heterojunction layer; a conditioninglayer such as LiF; and a cathode such as for example Ca, Al, or Ba.Devices can be adapted to allow for current density versus voltagemeasurements.

Similarly, OLED devices are known in the art as illustrated in forexample FIG. 9. The devices can comprise, for example, multi-layerstructures including for example an anode such as ITO on glass or PET orPEN; a hole injection layer; an electroluminescent layer such as apolymer layer; a conditioning layer such as LiF, and a cathode such asfor example Ca, Al, or Ba.

Methods known in the art can be used to fabricate devices including forexample OLED and OPV devices. Methods known in the art can be used tomeasure brightness, efficiency, and lifetimes. OLED patents include forexample U.S. Pat. Nos. 4,356,429 and 4,539,507 (Kodak). Conductingpolymers which emit light are described in for example U.S. Pat. Nos.5,247,190 and 5,401,827 (Cambridge Display Technologies). See also Kraftet al., “Electroluminescent Conjugated Polymers—Seeing Polymers in a NewLight,” Angew. Chem. Int. Ed., 1998, 37, 402-428, including devicearchitecture, physical principles, solution processing, multilayering,blends, and materials synthesis and formulation, which is herebyincorporated by reference in its entirety.

Light emitters known in the art and commercially available can be usedincluding various conducting polymers as well as organic molecules, suchas materials available from Sumation, Merck Yellow, Merck Blue, AmericanDye Sources (ADS), Kodak (e.g, A1Q3 and the like), and even Aldrich suchas BEHP-PPV. Examples of such organic electroluminescent materialsinclude:

(i) poly(p-phenylene vinylene) and its derivatives substituted atvarious positions on the phenylene moiety;

(ii) poly(p-phenylene vinylene) and its derivatives substituted atvarious positions on the vinylene moiety;

(iii) poly(p-phenylene vinylene) and its derivatives substituted atvarious positions on the phenylene moiety and also substituted atvarious positions on the vinylene moiety;

(iv) poly(arylene vinylene), where the arylene may be such moieties asnaphthalene, anthracene, furylene, thienylene, oxadiazole, and the like;

(v) derivatives of poly(arylene vinylene), where the arylene may be asin (iv) above, and additionally have substituents at various positionson the arylene;

(vi) derivatives of poly(arylene vinylene), where the arylene may be asin (iv) above, and additionally have substituents at various positionson the vinylene;

(vii) derivatives of poly(arylene vinylene), where the arylene may be asin (iv) above, and additionally have substituents at various positionson the arylene and substituents at various positions on the vinylene;

(viii) co-polymers of arylene vinylene oligomers, such as those in (iv),(v), (vi), and (vii) with non-conjugated oligomers; and

(ix) polyp-phenylene and its derivatives substituted at variouspositions on the phenylene moiety, including ladder polymer derivativessuch as poly(9,9-dialkyl fluorene) and the like;

(x) poly(arylenes) where the arylene may be such moieties asnaphthalene, anthracene, furylene, thienylene, oxadiazole, and the like;and their derivatives substituted at various positions on the arylenemoiety;

(xi) co-polymers of oligoarylenes such as those in (x) withnon-conjugated oligomers;

(xii) polyquinoline and its derivatives;

(xiii) co-polymers of polyquinoline with p-phenylene substituted on thephenylene with, for example, alkyl or alkoxy groups to providesolubility; and

(xiv) rigid rod polymers such as poly(p-phenylene-2,6-benzobisthiazole),poly(p-phenylene-2,6-benzobisoxazole),polyp-phenylene-2,6-benzimidazole), and their derivatives.

Preferred organic emissive polymers include SUMATION Light EmittingPolymers (“LEPs”) that emit green, red, blue, or white light or theirfamilies, copolymers, derivatives, or mixtures thereof; the SUMATIONLEPs are available from Sumation KK. Other polymers includepolyspirofluorene-like polymers available from Covion OrganicSemiconductors GmbH, Frankfurt, Germany (now owned by Merck).

Alternatively, rather than polymers, small organic molecules that emitby fluorescence or by phosphorescence can serve as the organicelectroluminescent layer. Examples of small-molecule organicelectroluminescent materials include: (i) tris(8-hydroxyquinolinato)aluminum (Alq); (ii) 1,3-bis(N,N-dimethylaminophenyl)-1,3,4-oxidazole(OXD-8); (iii)-oxo-bis(2-methyl-8-quinolinato)aluminum; (iv)bis(2-methyl-8-hydroxyquinolinato) aluminum; (v)bis(hydroxybenzoquinolinato) beryllium (BeQ.sub.2); (vi)bis(diphenylvinyl)biphenylene (DPVBI); and (vii) arylamine-substituteddistyrylarylene (DSA amine).

Such polymer and small-molecule materials are well known in the art andare described in, for example, U.S. Pat. No. 5,047,687 issued toVanSlyke; and Bredas, J.-L., Silbey, R., eds., Conjugated Polymers,Kluwer Academic Press, Dordrecht (1991).

Examples of HIL in devices include:

1) Hole injection in OLEDs including PLEDs and SMOLEDs; for example, forHIL in PLED, all classes of conjugated polymeric emitters where theconjugation involves carbon or silicon atoms can be used. For HIL inSMOLED, the following are examples: SMOLED containing fluorescentemitters; SMOLED containing phosphorescent emitters; SMOLEDs comprisingone or more organic layers in addition to the HIL layer; and SMOLEDswhere the small molecule layer is processed from solution or aerosolspray or any other processing methodology. In addition, other examplesinclude HIL in dendrimer or oligomeric organic semiconductor basedOLEDs; HIL in ambipolar light emitting FET's where the HIL is used tomodify charge injection or as an electrode in2) Hole extraction layer in OPV:3) Channel material in transistors4) Channel material in circuits comprising a combination of transistorssuch as logic gates5) Electrode material in transistors6) Gate layer in a capacitor7) Chemical sensor where modification of doping level is achieved due toassociation of the species to be sensed with the conductive polymer.

A variety of photoactive layers can be used in OPV devices. Photovoltaicdevices can be prepared with photoactive layers comprising fullerenederivatives mixed with for example conducting polymers as described infor example U.S. Pat. Nos. 5,454,880 (Univ. Cal.); 6,812,399; and6,933,436.

Common electrode materials and substrates, as well as encapsulatingmaterials can be used.

OLED Measurements

Methods known in the art can be used to measure OLED parameters. Forexample, measurements can be carried out at 10 mA/cm².

Voltage can be for example about 2 to about 8, or about 3 to about 7including for example about 2 to about 5.

Brightness can be, for example, at least 250 cd/m², or at least 500cd/m², or at least 750 cd/m², or at least 1,000 cd/m².

Efficiency can be, for example, at least 0.25 Cd/A, or at least 0.45Cd/A, or at least 0.60 Cd/A, or at least 0.70 Cd/A, or at least 1.00Cd/A, or at least 2.5 Cd/A, or at least 5.00 Cd/A, or at least 7.50Cd/A, or at least 10.00 Cd/A.

Lifetime can be measured at 50 mA/cm² in hours and can be, for example,at least 50 hours, or at least 100 hours, or at least about 900 hours,or at least 1,000 hours, or at least 1100 hours, or at least 2,000hours, or at least 5,000 hours.

Combinations of brightness, efficiency, and lifetime can be achieved.For example, brightness can be at least 1,000 cd/m2, efficiency can beat least 1.00 Cd/A, and lifetime can be at least 1,000 hours, at least2,500 hours, or at least 5,000 hours.

OPV Measurements

Methods known in the art can be used to measure OPV parameters.

J_(SC) values (mA/cm²) can be for example at least 6, or at least 7, orat least 8, or at least 9, or at least 10, or at least 11, or at least12. The values can be for example about 5 to about 12, or about 5 toabout 15, or about 5 to about 20.

V_(OC) values (V) can be for example at least about 0.5, or at leastabout 0.6, or at least about 0.7, or at least about 0.8, or at leastabout 0.9, or at least about 1.0, including for example about 0.5 toabout 1.0, or about 0.55 to about 0.65.

FF values can for example at least about 0.2, or at least about 0.3, orat least about 0.4, or at least about 0.5, or at least about 0.6, or atleast about 0.7, including also for example about 0.5 to about 0.8, orabout 0.5 to about 0.73.

E (%) values can be for example at least about 1%, or at least about 2%,or at least about 3%, or at least about 4%, or at least about 5%, or atleast about 6%, or at least about 7%, including for example about 1% toabout 8%, or about 1% to about 7%, or about 1% to about 6%, or about 1%to about 5%, or about 1% to about 3.4%, or about 2% to about 3.4%.

Sulfonated polymers and formulations thereof as described herein can bemade into an ink that can be used to produce high-performancehole-extraction layer for organic photovoltaic devices. For example, theefficiency of 3.38% in the working examples was essentially the same asthe Baytron AI4083 control device in the same fabrication run. HILlayers can conduct holes and mediate hole-extraction as well as currentincumbent materials.

Control materials can be formulated such as PEDOT materials described inU.S. Pat. No. 4,959,430 to Jonas et al. Baytron materials can beobtained from H. C. Stark. Carbazole compounds are described in forexample WO 2004/072205 to Brunner et al.

Degradation rate can be also examined (see for example FIG. 16).Degradation time until normalized power output is zero for a cellsubstantially similar to that of FIG. 16 and for the conditionsdescribed therefore can be for example at least 250 hours, or at least300 hours, or at least 400 hours, or at least 500 hours.

Other types of devices which interact with light and orelectricity/electric fields can be fabricated including sensors andtransistors including field effect transistors (e.g., as electrodes oras active channel material, e.g., for use in logic circuits and otherelectronic circuitry). In particular, pH sensors, or sensors which aresensitive to detection of compounds which have functionalities which canbind to acid can be made and used in for example an optical sensingtool. Other device applications include for example supercapacitors(e.g., light weight power sources functioning as storage media with goodcharge capacity), cation transducers (e.g., devices featuring a cationbinding event causing an optical or electrical signal), drug release(e.g., drugs with ionic functionalities can be bound to the polymer anda redox chemistry can trigger the release of the drug into the body; oran embedded microchip with the polymer can help trigger the release ofthe drug into the body by changing the doping profile), electrochromics,actuators (e.g., electrochemical doping/de-doping also can change thevolume of the polymer which is the basis for actuating mechanism.Applications based on this can involve artificial muscles activated byelectrical pulse, or also smart membranes with tunable pore size forpurification of solvents), transparent electrodes to replace for exampleITO, and membranes.

Additional description for applications is provided:

For electrochromics applications and devices, including mirrors, see forexample Argun et al., Adv. Mater. 2003, 15, 1338-1341 (all polymericelectrochromic devices). For example, the sulfonated polymer exhibitsvery good stability in the oxidized form (i.e., very clear in thevisible region). Mirrors with good stability in the clear state can bemade. Only when a car with intense head-lamps approaches will themirrors will be activated to become dark. If the polymer can return toits oxidized form by itself it can be very advantageous as it willrequire no power to return its normal state. Since it absorbs strongly,through the NIR (which is the heating radiation) windows coated withthis polymer can potentially keep rooms cooler at the same time allowinglight to penetrate into the building, spacecrafts etc., potentiallyminimizing the load on the ACs and lights.

For sensors, change in conductivity, charge transport properties, and/oroptical properties can be made to occur due to specific interactions ofmaterial to be sensed with the HIL formulation; the signal can bedetected in sensors.

For photovoltaics, see for example Zhang et al. (polymer photovoltaiccells with conducting polymer anodes) Adv. Mater. 2002, 14, 662-665.

For speakers: see for example Lee, et al. (Flexible and transparentorganic film speaker by using highly conducting PEDOT/PSS as electrode),Synth. Met. 2003, 139, 457-461.

Electrostatic Dissipation Applications

Electrostatic dissipation coatings are described in for example U.S.provisional application Ser. No. 60/760,386 filed Jan. 20, 2006 to Grecoet al. (see also PCT application PCT/US2007/001245 filed Jan. 18, 2007),which are each hereby incorporated by reference in their entiretyincluding figures, claims, and working examples.

In one embodiment, regioregular polythiophene compositions as describedand claimed herein are employed in or as electrostatic dissipation (ESD)coatings, packaging materials, and other forms and applications.Electrostatic discharge is a common problem in many applicationsincluding electronic devices which are becoming smaller and moreintricate. To combat this undesired event, conductive coatings, alsoknown as ESD coatings, can be used to coat numerous devices and devicecomponents. Conductive materials can be also blended into othermaterials such as polymers to form blends and packaging materials. Theregrioregular polythiophenes or polymers comprising regioregularpolythiophenes described herein may be used as the only polymericcomponent of an ESD coating or be combined (i.e. blended) with one ormore polymers which do not comprise regioregular polythiophenes.Furthermore, the regioregular polythiophenes can be a homopolymer, acopolymer or a block copolymer.

A non-limiting example of this embodiment involves a device comprisingan electrostatic dissipation (ESD) coating, said ESD coating comprisingat least one water soluble or water dispersible polymer comprisingregioregular polythiophene comprising: at least one organic substituent;and at least one sulfonated substituent comprising sulfur bondingdirectly to the polythiophene backbone. In another embodiment, providedis an ESD packaging material.

In another embodiment, the coating may be a blend of one or morepolymers wherein at least one comprises regioregular polythiophene.Further, in addition to one polymer comprising regioregularpolythiophene, the ESD coating can comprise at least one polymer withoutregioregular polythiophene. In these ESD coatings, where a polymericblend is used, the polymers are preferably compatible.

The molecular weight of the polymers in the coating can vary. Ingeneral, for example, the number average molecular weight of the polymercomprising regioregular polythiophene, the polymer without regioregularpolythiophene, or both can be between about 5,000 and about 50,000. Ifdesired, the number average molecular weight of the polymer withoutregioregular polythiophene can be for example about 5,000 to about10,000,000, or about 5,000 to about 1,000,000.

In any of the aforementioned ESD coatings, at least one polymer may becross-linked for various reasons such as improved chemical, mechanicalor electrical properties.

Regioregularity of the polythiophene may be, for example, at least about85%, or at least about 95%, or at least about 98%. In some embodiments,the degree of regioregularity can be at least about 70%, or at leastabout 80%. For example, in some instances, including some ESDapplications, cost may be important and the highest levels ofregioregularity may not be needed to achieve the performance. The ESDcoating also preferably contains less that about 50 wt. %, or less thanabout 30 wt. % regioregular polythiophene polymer. The minimum amount ofthe polymer can be for example about 0.1 wt. % or about 1 wt. % or about10 wt. %.

The polymer which does not comprise regioregular polythiophene can be asynthetic polymer and is not particularly limited. It can be for examplethermoplastic. It can be a water soluble polymer or a polymer capable ofaqueous based dispersion. Examples include organic polymers, syntheticpolymers polymer or oligomer such as a polyvinyl polymer having apolymer side group, a poly(styrene) or a poly(styrene) derivative,poly(vinyl acetate) or its derivatives, poly(ethylene glycol) or itsderivatives such as poly(ethylene-co-vinyl acetate), poly(pyrrolidone)or its derivatives such as poly(1-vinylpyrrolidone-co-vinyl acetate,poly(vinyl pyridine) or its derivatives, poly(methyl methacrylate) orits derivatives, poly(butyl acrylate) or its derivatives. Moregenerally, it can comprise of polymers or oligomers built from monomerssuch as CH₂CH Ar, where Ar=any aryl or functionalized aryl group,isocyanates, ethylene oxides, conjugated dienes, CH₂CHR₁R (whereR₁=alkyl, aryl, or alkyl/aryl functionality and R=H, alkyl, Cl, Br, F,OH, ester, acid, or ether), lactam, lactone, siloxanes, and ATRPmacroinitiators. Preferred examples include poly(styrene) andpoly(4-vinyl pyridine). Another example is a water-soluble orwater-dispersable polyurethane.

For proper dissipation of static electricity the conductivity of thecoating can be tuned. For example, the amount of conductive material canbe increased or decreased. In addition, in some cases, doping can beused although the self-doping nature of the sulfonated polymer providesdoping. Further doping may be achieved via organic, inorganic or ambientspecies and in forms of solids, liquids, gases, or a combinationthereof. Oxidation is a useful method of enhancing electricalconductivity of polythiophenes. Useful halogen dopants include Br, I,Cl. Inorganic dopants include compounds that may be represented by irontrichloride, gold trichloride, arsenic pentafluoride, alkali metal saltsof hypochlorite, protic acids such as benzenesulfonic acid andderivatives thereof, propionic acid, organic carboxylic and sulfonicacids, nitrosonium salts, NOPF₆ or NOBF₄, organic oxidants,tetracyanoquinone, dichlorodicyanoquinone, hypervalent iodine oxidants,iodosylbenzene, iodobenzene diacetate or a combination thereof.Including certain polymers in the blend can also lead to a doping effectin the polythiophenes. For instance, a polymer comprising an oxidativefunctionality, acidic functionality, poly(styrene sulfonic) acid or acombination thereof can be also included in the coating. Other compoundsthat provide a doping effect include: certain Lewis acids, irontrichloride, gold trichloride, and arsenic pentafluoride, protic organicacids, inorganic acids, benzenesulfonic acids and derivatives thereof,propionic acid, organic carboxylic acids, sulfonic acids, mineral acids,nitric acids, sulfuric acids, hydrochloric acids, tetracyanoquinone,dichlorodicyanoquinone, hypervalent iodine, iodosylbenzene, iodobenzenediacetate. Ambient doping typically occurs via species in the ambientair such as oxygen, carbon dioxide and moisture. The polymer comprisingregioregular polythiophene is preferably doped sufficiently to providean electronic conductivity in the material of at least about 10⁻¹⁰siemens/cm (S/cm) or between about 10⁻¹³ siemens/cm to about 10⁻³siemens/cm. The ESD coating preferably should retain efficacy over thelifetime of the device. Roughly, in certain cases it is desirable thatthe coating retain electronic conductivity of at least 10⁻¹³ for atleast 1000 hrs.

In one example the regioregular polythiophene is doped with a quinonecompound and the coating has a thickness of about 10 nm to about 100 nm,and wherein the polymer which does not comprise regioregularpolythiophene comprises a polystyrene, a polystyrene derivative, apolyurethane, a polyacrylate, a polypyridine, or a polyvinyl phenol.

Application of the ESD coating can be achieved via spin coating, inkjetting, roll coating, gravure printing, dip coating, zone casting, or acombination thereof. Normally the applied coating is greater than 10 nmin thickness. Often, the coating is applied to insulating surfaces suchas glass, silica, polymer or any others where static charge builds up.Additionally, the conductive polymer can be blended into materials usedto fabricate packaging film used for protection of for example sensitiveelectronic equipment. This may be achieved by typical processingmethodologies such as for example blown film extrusion. Opticalproperties of the finished coating can vary tremendously depending onthe type of blend and percent ratio of the polythiophene polymers.Preferably, transparency of the coating is at least 90% over thewavelength region of 300 nm to 800 nm.

The ESD coatings can be applied to a wide variety of devices requiringstatic charge dissipation. Non-limiting examples include: semiconductordevices and components, integrated circuits, display screens,projectors, aircraft wide screens, vehicular wide screens or CRTscreens.

In one embodiment, an ESD coating is formulated from an aqueous solutionof sulfonated conducting polymer. The pH can be adjusted to aboutneutral with a basic compound such as an amine. Water as well as anaqueous solution of a second polymer can be added. A non-aqueous solventcan be used to improve dispersion. See working example below. The weightpercentage of conducting polymer such as sulfonated polythiophene in thefinal solids can be for example about 2 wt. % to about 30 wt. %, orabout 5 wt. % to about 20 wt. %. Water content in the solution beforeremoval of solvent can be for example about 40 wt. % to about 80 wt. %in solution.

In addition, the sulfonated polymers described herein can be used intransparent electrode applications.

WORKING EXAMPLES

Further description is also provided by way of the followingnon-limiting working examples.

Working Example 1 Synthesis by Sulfuric Acid Preparation of sulfonatedpoly(3-(methoxyethoxyethoxy)thiophene-2,5-diyl) (P3MEET-S, or MPX)

6.02 g of neutral poly(3-(methoxyethoxyethoxy)thiophene-2,5-diyl)(Mw=15,000; PDI=1.4) was stirred at 80-85° C. in 180 mL fuming sulfuricacid (Acros) for 24 hours and added to 6 L de-ionized water. The aqueousdispersion was stirred for an hour and centrifuged. The clearsupernatant was removed and 800 mL fresh de-ionized water was added tothe centrifugate, shaken vigorously and centrifuged again. The clearsupernatant was removed and the process was repeated two more times. Thewet polymer was diluted with de-ionized water to make the total solidscontent between 0.5 and 1% and sonicated for 30 min. The suspension wasthen passed in 2 lots through a glass column (1″ diameter) packed with30 g of fresh Amberjet 4400 (OH form, Aldrich) ion-exchange resin, foreach lot. This process removed any residual free sulfuric acid. Theaqueous suspension of the sulfonated polymer thus obtained did not showany aggregation or precipitation even after several days of storageunder ambient conditions at these concentrations.

The acid equivalent was determined to be 74.4 mg NaOH per gram ofsulfonated polymer. Elemental analysis (CHS) of the polymer was done atGalbraith Laboratories Inc. and the CHS content was determined to be43.22, 3.37 and 23.44% by weight, respectively. Based on the C/S ratio,the sulfonation level was determined to be 83%.

See FIGS. 1 and 2.

Working Example 2 Synthesis of Another Polythiophene Sulfonation ofpoly(3-(ethyloxyethoxyethoxyethoxy)thiophene-2,5-diyl)

Sulfonated poly(3-(ethyloxyethoxyethoxyethoxy)thiophene-2,5-diyl) wasprepared using a similar procedure as shown in example 2. UV-Vis-NIRspectra resembles that of for the polymer of Example 1 characterized bya strong absorbance throughout the NIR region indicative of abipolaronic character.

Working Example 3 Synthesis by Alternative Reagent Sulfonation ofpoly(3-(methyloxyethoxyethoxy)thiophene-2,5-diyl)

Alternatively, sulfonation can also be carried out by dissolvingpoly(3-(methyloxyethoxyethoxy)thiophene-2,5-diyl) in chloroform andadding acetyl sulfate reagent prepared in situ in anhydrous1,2-dichloroethane as reported by Makoski H. S. and Lundberg, R. U.S.Pat. No. 3,870,841, 1975. 1.0 gmpoly(3-(methyloxyethoxyethoxy)thiophene-2,5-diyl) was heated to refluxwith 50 mL chloroform. To this solution 3.4 mL of acetyl sulfate (1 eq)reagent was added. The reaction mixture was refluxed for 27 h and addedto 200 mL methanol, followed by filtering, washing with de-ionized waterto neutral pH and finally with methanol before drying to a fine powder.

Working Example 4 Synthesis with Ion Exchange

Tetra-n-butylammonium salt of P3MEET-S was prepared by adding 42.3 mg ofn-Bu₄NOH.30H₂O to 5.027 g of 0.6% aqueous P3MEET-S. This represents 0.95eq of free acid based on previous titration results, see Example 1. pHof the solution was measured to be 4.30 after adding the n-Bu₄NOH.30H₂O(called T1). pH of as prepared P3MEET-S was 3.165. Similarly, anothersolution with 88.8 mg n-Bu₄NOH.30H₂O was added to 5.002 g of 0.6%aqueous P3MEET-S. pH of this solution was measured to be 11.2 (calledT2).

See FIG. 3.

Working Example 5 Synthesis of Bisthiophene Polymer Sulfonation ofpoly(3,3′-bis-[2-(2-methoxy-ethoxy)-ethoxy]-[2,2′]bithiophene-5,5′-diyl))

Poly(3,3′-bis-[2-(2-methoxy-ethoxy)-ethoxy]-[2,2′]bithiophene-5,5′-diyl))was prepared using a similar procedures as shown in example 1. See FIG.4.

Synthesis of 3,3′-bis-[2-(2-methoxy-ethoxy)-ethoxy]-[2,2′]bithiophene

3,3′-bis-[2-(2-methoxy-ethoxy)-ethoxy]-[2,2′]bithiophene was prepared bya procedure adopted from the preparation of2,2′-Bis(3,4-ethylenedioxythiophene) (BiEDOT) reported by Sotzing et al(Adv. Mater. 1997, 9, 795). 3-[2-(2-Methoxy-ethoxy)-ethoxy]-thiophenewas lithiated at −78° C. followed by coupling using anhydrous CuCl₂. Thefinal product was isolated via column chromatography using 1:1 (v/v)ethyl acetate/hexanes as the eluent. 1H-NMR (CDCl3, δ ppm):

Synthesis ofpoly(3,3′-bis-[2-(2-methoxy-ethoxy)-ethoxy]-[2,2′]bithiophene-5,5′-diyl)

2.5 gms of 3,3′-bis-[2-(2-methoxy-ethoxy)-ethoxy]-[2,2′]bithiophenedissolved in 25 mL chloroform was added to a 1 L three-neck RBF. To thissolution 2.5 gms of FeCl₃ (2.5 eq) dissolved in 350 mL chloroform wasadded dropwise over 2.5 hrs. The reaction mixture was stirred at roomtemperature for 14 hours. The oxidized polymer solids were filtered, andstirred in 200 mL 9:1 (v/v) MeOH+ Conc. HCl for 1 h. The next step wasto filter and repeat process to remove any free iron salts. The solids(˜2 gms) were added to 100 mL chloroform followed by 15 mL of aqueoussolution of hydrazine (35 wt %). Reflux was carried out for 30 min.Addition of hydrazine caused the polymer to dissolve in chloroform. Thesolution was poured into 1 L methanol+100 mL water, and stirred for anhour and filtered. The filtered solids were stirred in 150 mL water at50° C. for 1 h and filtered. The solids were added to 180 mL water plus10 mL Conc. HCl and heated for 1 h at 50° C., filtered and dried in ovenat RT for 2 days. Conductivities of iodine doped 337 nm thick drop castfilms were measured to be 1 Scm⁻¹. GPC analysis using chloroform aseluent and a UV-vis detector (λ=420 nm) gave a Mn=12707 (PDI=5).

Working Example 6 Characterization of Films

6A. FIG. 5 shows the Vis-NIR spectrum of a doped film of the sulfonatedpoly(3-(methoxyethoxyethoxy)thiophene-2,5-diyl) spin-coated onto glassplates. The films were annealed at 150° C. for 15 min after spincoating. These films exhibited very strong absorbance extending into theNIR region, typical of oxidized conjugated polymers. The spectrumunderwent little/no change even after 7 days of storage under ambientconditions demonstrating the excellent stability in the oxidized form.

6B. FIG. 6 shows spectra of thin films prepared by spinning the abovesolutions of T1 and T2 onto a glass plate (form working example 4). Thefilms were annealed at 150° C. for 10 min before obtaining the spectra.

Working Examples 7-11 Formulations Example 7

A solution of Plexcore MPX in water (about 0.61% by weight) was preparedas described above in Example 1. This solution (4.92 g) was added to avial along with water (4.81 g) and placed in an ultrasonic bath for 30minutes. Poly(4-vinylphenol) (0.27 g) was dissolved in 2-butoxyethanol(6.00 g) and heated with stirring until the polymer dissolvedcompletely. The two solutions were then combined and mixed thoroughly.The solution was then passed through a 0.22 micron PVDF syringe filter(Millipore).

Examples 8 and 9

The procedure was similar to that of Example 7 except that an aqueousdispersion of polystyrenesulfonic acid (PSS) was added after theaddition of poly(4-vinylphenol).

Example 10

The procedure was similar to that of Example 7 except that PSS was addedin place of the poly(4-vinylphenol).

Example 11A

The procedure is identical to Example 7 except that an aqueousdispersion of NeoRez R-966 (an aliphatic urethane dispersion fromAvecia) was added in place of the poly(4-vinylphenol) (PUD ispolyurethane dispersion).

Example 11B

The procedure is identical to Example 7 except that Nafion®perfluorinated ion-exchange resin (10% dispersion) was added after theaddition of poly(4-vinylphenol). See also Example 11C for use ofNafion®.

Plex- Poly(4- Ex- 2-Butoxy- core vinyl ample Water ethanol MPX phenol)PSS Nafion PUD  7 9.70 6.00 0.030 0.272 — — —  8 9.63 6.00 0.030 0.2560.015 — —  9 9.63 6.00 0.045 0.241 0.015 — — 10 9.63 6.00 0.015 — 0.286— — 11A 8.40 0.93 0.030 — — — 0.64 11B 8.07 6.60 0.019 0.294 — 0.017 —11C 6.84 7.78 0.020 0.297 0.0124 0.001 —

Additional formulations were made as follows:

Syn- Syn- thetic thetic ICP polymer polymer Synthetic Poly- 1 2 polymer3 mer PV4P PSS NAFION Solvent 1 Solvent 2 11D 6 89 5 0 Water(55) Butylcellosolve(45) 11E 6 89 0 5 Water(55) Butyl cellosolve(45) 11F 6 92 1 1Water(55) Butyl cellosolve(45)

Examples 12-14 Photovoltaic Device

The device fabrication described below is intended as an illustrativeexample and does not in any way imply the limitation of the invention tothe said fabrication process, device architecture (sequence, number oflayers etc.) or materials other than the HIL materials claimed in thisinvention.

The OPV devices described herein were fabricated on indium tin oxide(ITO) surfaces deposited on glass substrates. The ITO surface waspre-patterned to define the pixel area of 0.9 cm². The device substrateswere cleaned by ultrasonication in a dilute soap solution, followed bydistilled water for 20 minutes each. This was followed byultrasonication in isopropanol. The substrates were dried under nitrogenflow, following which they were treated in a UV-Ozone chamber operatingat 300 W for 20 minutes.

The cleaned substrates were then coated with the hole collection layer.The coating process was done on a spin coater but can be similarlyachieved with spray coating, ink-jetting, contact printing or any otherdeposition method capable of resulting in an HCL film of the desiredthickness. An HIL ink (from Examples 7, 8, or 9) was spin-coated andthen dried at 175° C. for 30 minutes resulting in a 170 nm thick layer.The active layer (a 2:1 weight ratio blend of P3HT/PCBM(methanofullerene [6,6]-phenyl C61-butyric acid methyl ester) wasapplied by spin coating in a nitrogen atmosphere and annealed at 175° C.for 30 minutes resulting in a 200 nm thick layer. This film was spun ontop of the HIL film with no observable morphological damage to the HIL(independently verified by atomic force microscopy, AFM). The substrateswere then transferred to a vacuum chamber in which, by means of physicalvapor deposition, a cathode layer was deposited. In this example, thecathode layer was prepared by the sequential deposition of two metallayers, the first being a 5 nm layer of Ca (0.1 nm/sec) followed by a200 nm layer of Al (0.5 nm/sec) with the base pressure at 5×10⁻⁷ Torr.

The devices thus obtained were encapsulated with a glass cover slip toprevent exposure to ambient conditions by means of a UV-light curingepoxy resin cured at 80 W/cm² UV exposure 4 minutes.

Example 15 OPV Testing

The OPVs fabricated in this example are representative of the formatthey may be used in actual applications all of which are considered tobe covered by this invention, limited only by the presence of the HILdisclosed herein being present in the device stack. The testing exampleas described below is used only to describe the evaluation of the OPVperformance and is not considered to be the only methodology utilized toelectrically address the OPV.

The OPVs comprise pixels on a glass substrate whose electrodes extendoutside the encapsulated area of the device which contain the lightharvesting portion of the pixels. The typical area of each pixel was0.09 cm². The electrodes were contacted with a current source meter suchas a Keithley 2400 source meter with a bias applied to the indium tinoxide electrode while the aluminum electrode is earthed. The device wasthen held under the plane wave front of an Oriel 300 W Solar simulatorequipped with a Xenon lamp at a distance of ˜20 cm from the optics ofthe Solar simulator. The optical power of the light incident on thepixel was 100 mW/cm², while the actual spectrum of the light generatedby the Solar simulator approximates the light generated by the Sun,which corresponds to the standard Air Mass 1.5 Global Filter or AM 1.5Gspectrum.

The pixel thus illuminated absorbs light and generates photocurrent.This photocurrent comprises positive charges (holes) and negativecharges (electrons) which are collected by the electrodes depending onthe electrically applied bias. This photocurrent was in turn read by theKeithley 2400 source meter. Thus the generated photocurrent was measuredas a function of the voltage applied to the pixel. The short circuitcurrent (the current generated under illumination at zero volts bias) isindicative of the efficiency with which holes are extracted by the holeextraction layer. Besides this, the open circuit voltage and the fillfactor together with the short circuit current determine the overallefficiency of the device.

FIG. 7 illustrates a typical conductive polymer photovoltaic cell. FIG.8 illustrates representative data. The following Table I providesadditional data:

TABLE I Jsc (mA/cm2) Voc (V) FF E (%) PEDOT 10.84 0.60 0.55 3.59 Example7 9.59 0.59 0.24 1.38 Example 8 9.72 0.59 0.38 2.14 Example 9 10.34 0.590.55 3.38 Example 10 6.72 0.59 0.29 1.16

The efficiency reported in FIG. 8 (3.38%) was essentially the same asthe Baytron AI4083 control device in the same fabrication run (theincumbent material).

FIG. 16 illustrates degradation of power output of organic photovoltaiccells made with CH8000 and Example 11B as the hole extraction layer. Thedevices are placed under a lamp generating 2 suns of light output andare operating at a temperature of 85° C.

Working Example OLED Device Fabrication

The device fabrication described below is intended as an example anddoes not in any way imply the limitation of the invention to the saidfabrication process, device architecture (sequence, number of layersetc.) or materials other than the HIL materials claimed in thisinvention.

The OLED devices described herein were fabricated on indium tin oxide(ITO) surfaces deposited on glass substrates. The ITO surface waspre-patterned to define the pixel area of 0.9 cm². The device substrateswere cleaned by ultrasonication in a dilute soap solution followed bydistilled water for 20 minutes each. This was followed byultrasonication in isopropanol. The substrates were dried under nitrogenflow, following which they were treated in a UV-Ozone chamber operatingat 300 W for 20 minutes.

The cleaned substrates were then coated with the hole injection layerand dried at 200° C. for 15 minutes (60 nm dry film thickness). Thecoating process was done on a spin coater but can be similarly achievedwith spray coating, ink-jetting, contact printing or any otherdeposition method capable of resulting in an HIL film of the desiredthickness. This was followed by the spin coating of the light emittingpolymer (LEP) layer which was dried at 170° C. for 15 minutes (75 nm dryfilm thickness).

The substrates were then transferred to a vacuum chamber in which, bymeans of physical vapor deposition, a cathode layer was deposited. Inthis example, the cathode layer was prepared by the sequentialdeposition of two metal layers, the first being a 5 nm layer of Ca (orBa) (0.1 nm/sec) followed by a 200 nm layer of Al (0.5 nm/sec) with thebase pressure at 5×10⁻⁷ Torr.

The devices thus obtained were encapsulated with a glass cover slip toprevent exposure to ambient conditions by means of a UV-light curingepoxy resin cured at 80 W/cm² UV exposure for 4 minutes.

Hybrid—SMOLED Device Fabrication:

The device fabrication described below is intended as an example anddoes not in any way imply the limitation of the invention to the saidfabrication process, device architecture (sequence, number of layersetc.) or materials other than the HIL materials claimed in thisinvention.

The representative device is an example of hybrid device architectureinvolving a solution processed hole injection layer (HIL) and avapor-deposited hole transport layer ofN,N′-di(naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB) and electrontransport layer (ETL) and emissive layer oftris(8-hydroxyquinolinato)aluminum (ALQ3) with pre-patterned ITO asanode and LiF and Al as cathode.

The hybrid SMOLED devices described herein were fabricated on indium tinoxide (ITO) surfaces deposited on glass substrates. The ITO surface waspre-patterned to define the pixel area of 0.9 cm². The device substrateswere cleaned by ultrasonication in a dilute soap solution followed bydistilled water for 20 minutes each. This was followed byultrasonication in isopropanol. The substrates were dried under nitrogenflow, after which they were treated under a UV-Ozone chamber operatingat 300 W for 20 minutes.

The cleaned substrates were then coated with the hole injection layer(HIL). The coating process was done on a spin coater but can easily besimilarly achieved with spray coating, ink-jetting, contact printing orany other deposition method capable of resulting in an HIL film of thedesired thickness. The spin-coated HIL was annealed at 200° C. for 15minutes in an inert glove box environment resulting in a 60 nm filmthickness.

The substrates were then transferred to a vacuum deposition chamber inwhich by means of physical thermal deposition the organic materials—NPBas hole transport layer and ALQ3 as electron transport and emissivelayer—were deposited. The thickness of 70 nm was achieved for both NPBand ALQ3 layers respectively. This was followed by deposition of thecathode in the form of a sequential deposition of two metal layers, thefirst layer being the LiF layer of 0.5 nm thickness followed by a 200 nmlayer of Al. The following Table summarizes the deposition parametersfor the device fabrication:

Typical base pressure at start of the run: 5.0×10⁻⁷ torr

Deposition Rate* Final Thickness Material (nm/Sec) (nm) NPB 0.46-0.48 70ALQ3 0.41-0.55 70 LiF 0.02-0.03 0.5 Al 0.4-0.6 200 *Typical Range

The devices thus obtained were encapsulated with a glass cover slip toprevent exposure to ambient conditions by means of a UV-light curingepoxy resin cured at 80 W/cm² UV exposure for 4 minutes.

Device Testing (OLED/SMOLED):

The OLEDs fabricated in this example are representative of the formatthey may be used in actual applications all of which are considered tobe covered by this invention, limited only by the presence of the HILdisclosed herein being present in the device stack. The testing exampleas described below is used only to describe the evaluation of the OLEDperformance and is not considered to be the only methodology utilized toelectrically address the OLEDs.

The OLEDs comprise pixels on a glass substrate whose electrodes extendoutside the encapsulated area of the device which contain the lightemitting portion of the pixels. The typical area of each pixel is 0.09cm². The electrodes are contacted with a current source meter such as aKeithley 2400 source meter with a bias applied to the indium tin oxideelectrode while the aluminum electrode is earthed. This results inpositively charged carriers (holes) and negatively charged carriersbeing injected into the device which form excitons and generate light.In this example, the HIL assists the injection of charge carriers intothe light emitting layer. This results in a low operating voltage of thedevice (defined as the voltage required to run a given current densitythrough the pixel).

Simultaneously, another Keithley 2400 source meter is used to address alarge area silicon photodiode. This photodiode is maintained at zerovolts bias by the 2400 source meter. It is placed in direct contact witharea of the glass substrate directly below the lighted area of the OLEDpixel. The photodiode collects the light generated by the OLEDconverting them into photocurrent which is in turn read by the sourcemeter. The photodiode current generated is quantified into optical units(candelas/sq. meter) by calibrating it with the help of a Minolta CS-200Chromameter.

During the testing of the device, the Keithley 2400 addressing the OLEDpixel applies a voltage sweep to it. The resultant current passingthrough the pixel is measured. At the same time the current passingthrough the OLED pixel results in light being generated which thenresults in a photocurrent reading by the other Keithley 2400 connectedto the photodiode. Thus the voltage-current-light or IVL data for thepixel is generated. This in turn enables the measurement of other devicecharacteristics such as the lumens per Watt of electrical input power tothe pixel and candelas per ampere of pixel current.

FIG. 9 illustrates a schematic representation of an organic lightemitting diode (OLED). Table II and FIGS. 10-14 provide device testingdata.

The performance of different HILs in different example OLED types isdescribed. Note that typically performance is quantified by acombination of different parameters such as operating voltage (should below), brightness in nits (should be bright, luminous efficiency in unitsof cd/A (reflecting how much electric charge is needed to obtain lightfrom the device) and the lifetime under operation (time required toreach half of the initial luminance value at the start of the test). Assuch, the overall performance is very important in a comparativeevaluation of HIL performance. Below, the description is classified intodifferent sections depending on device type being evaluated.

-   -   1) OC1C10: As observed from the data in FIG. 10, depending on        the composition of HILs performance in voltage equal to that of        PEDOT and in case of efficiency even exceeding PEDOT can be        attained. Note that in these devices the efficiency is limited        by the emitter and not the HIL being used. Brightness of the        devices were as high as 1200 nits in case of Example 8 at 7V.    -   2) Commercial emitter 1: The emitter layer used in these devices        has a much higher intrinsic ability to harvest light from charge        carriers due to a high quantum efficiency. As a result, the        efficiencies in this case are as high as 8-11 cd/A as shown in        FIG. 11. FIG. 12 also indicates that depending on composition        both voltage and efficiency of example HILs discussed herein can        be tuned to equal that of PEDOT.    -   3) Commercial emitter 2: In the case of commercial emitter 2        (FIG. 12) a three layer device architecture where an additional        buffer layer is utilized between the HIL and the emissive layer        is used as a test device architecture. As observed, the        operating voltage, luminance and efficiencies for Example 7 are        comparable to that of PEDOT.    -   4) SMOLED Devices: FIG. 13 provides a summary of the performance        of different HILs in hybrid devices. The operating voltage of        the example HILs compare quite well with that obtained for        PEDOT. Furthermore as is evident from the efficiency data the        performance of all example HILs exceeds that of PEDOT. The most        important result which clearly demonstrated the superior        performance of the Example HILs is depicted in FIG. 14. The        graph shows the luminance decay over time as devices are        stressed at a constant DC current from an initial luminance of        1000 nits. As observed, there is a dramatic difference in        lifetime performance of Example 7 being used as an HIL compared        to PEDOT. While PEDOT has a half life of not more than 50-60        hrs, the device with Example 7 as the HIL shows no loss of        luminance on these time scales. As the device is tested for a        longer time it is expected that the luminance will eventually        decay. However, even with only 50 hours of data collected it is        already apparent that the performance of Example 7 far exceeds        that of PEDOT.

FIG. 17 illustrates current-voltage luminance performance for OC1C10based OLED devices comparing PEDOT and HIL 384.1 as described herein. Animprovement in efficiency is observed over PEDOT.

FIG. 18 illustrates current-voltage luminance performance for acommercial emitter 1 based OLED devices comparing CH8000 and Example11C. Comparable performance to CH8000 is obtained for this HIL asevident from the data.

FIG. 19 illustrates luminance decay under passive matrix testingconditions at 70 degrees Celsius for devices comprising a commercialemitter 1. Lifetime for the Example 11C containing device is observed tobe better than for CH8000.

FIG. 20 illustrates current-voltage-luminance performance for commercialemitter 2 based OLED devices comparing CH8000 and Example 11C.Comparable performance to CH8000 is obtained for this HIL as evidentfrom the data.

FIG. 21 illustrates luminance decay under passive matrix testingconditions for devices comprising a commercial emitter 2. Lifetime forthe HIL 665 device at room temperature is observed to be better thanthat for PEDOT. Even more dramatic is the lifetime performance at hightemperature. While the performance of PEDOT degrades at high temperaturethat of HIL 665 remains almost equivalent at 85 degrees Celsius comparedto room temperature performance.

FIG. 22 illustrates current-voltage-luminance performance for SMOLEDdevices comparing CH8000 and Example 7. Improved operating voltage isobtained with some loss in efficiency.

FIG. 23 illustrates comparison of luminance degradation for SMOLEDdevices including CH8000 and Example 7 at an initial luminance of 1,000nits under DC current at room temperature.

TABLE II Measured at 10 mA/cm2 Brightness Voltage (cd/m2) Efficiency HILSystem Emitter (Volts) (lm/W) (Cd/A) Baytron OC1C10 3.4 59 0.59 CH8000Example 7 OC1C10 3.5 38 0.38 Example 8 OC1C10 2.8 34 0.34 Example 9OC1C10 2.6 20 0.20 Example 10 OC1C10 3.7 66 0.66 Baytron Commercial 4.2712 7.1 CH8000 emitter 1 Example 7 Commercial 4.9 799 8.0 emitter 1Example 8 Commercial 4.3 817 8.2 emitter 1 Example 9 Commercial 4.6 7337.3 emitter 1 Example 10 Commercial 5.0 822 8.2 emitter 1 BaytronCommercial 3.8 1140 11.4 CH8000 Emitter 2 Example 7 Commercial 3.9 470.5 Emitter 2 Baytron Commercial 3.4 1406 14.1 CH8000 Emitter 2 (withinterlayer) Example 7 Commercial 3.6 1268 12.7 Emitter 2 (withinterlayer) Baytron SMOLED 5.1 209 2.1 CH8000 Example 7 SMOLED 5.5 2532.5 Example 8 SMOLED 6.7 237 2.4 Example 9 SMOLED 6.6 235 2.4 Example 10SMOLED 7.0 258 2.6

Working Example for ESD Coating Formulation

To a 20 mL vial was added a 0.57% aqueous sulfonated ICP solution (4.93g) and the pH adjusted to neutral with dimethylethanolamine. To thissolution was added DI water (3.78 g) and a polyurethane dispersion (0.84g, Witcobond W-240) with constant agitation. Butyl cellosolve (5.45 g)was then added and the solution was stirred vigorously on a hotplate for10 minutes at 75° C.

% in solution % in solids Sulfonated polymer 0.1875 10 Witcobond 2401.6875 90 DMEA 0.0154 Water 61.319 Butyl Cellosolve 36.791

1-98. (canceled)
 99. A method comprising: reacting a solubleregioregular polythiophene comprising (i) at least one organicsubstituent with a sulfonation reagent so that the polythiophenecomprises at least one sulfonate substituent comprising sulfonate sulfurbonding directly to the polythiophene backbone.
 100. The methodaccording to claim 99, wherein the sulfonation reagent is sulfuric acid.101. The method according to claim 99, wherein the sulfonation reagentis a sulfate compound.
 102. The method according to claim 99, whereinthe reacted polythiophene is doped.
 103. The method according to claim99, wherein the reacting results in a degree of sulfonation of at least10%.
 104. The method according to claim 99, wherein the reacting resultsin a degree of sulfonation of at least 50%.
 105. The method according toclaim 99, wherein the reacting results in a degree of sulfonation of atleast 75%.
 106. The method according to claim 99, wherein thesulfonation reagent is sulfuric acid, and the reacting results in adegree of sulfonation of at least 75%.
 107. The method according toclaim 99, wherein the sulfonation reagent is sulfuric acid, and thereacting results in a degree of sulfonation of at least 75%, and whereinthe polythiophene is a regio regular polythiophene having a degree ofregioregularity of at least about 90%.
 108. The method according toclaim 99, wherein the reacting results in a degree of sulfonation of atleast 50%, and wherein the polythiophene is a regio regularpolythiophene having a degree of regioregularity of at least about 98%.